Diastereoselective ortho-Metalation of a Chiral Ferrocenylphosphonic

Article pubs.acs.org/Organometallics

Diastereoselective ortho-Metalation of a Chiral Ferrocenylphosphonic Diamide and Its Organotin Derivatives Christina Dietz,† Viatcheslav Jouikov,‡,§ and Klaus Jurkschat*,† †

Lehrstuhl für Anorganische Chemie II, Fakultät Chemie der Technischen Universität Dortmund, D-44221 Dortmund, Germany UMR 6226 Molecular Chemistry and Photonics, University Rennes I, 35042 Rennes, France

‡

S Supporting Information *

ABSTRACT: The syntheses of the enantiopure ferrocenylphosphonic diamide (3aR,7aR)-2-ferrocenyl-3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-oxide ((R,R)FcP(O)(DMCDA), (R,R)-1) and its enantiomer (S,S)-FcP(O)(DMCDA) ((S,S)-1) are reported. Their ortho lithiation and subsequent treatment with Ph3SnCl selectively provided the corresponding tetraorganotin derivatives FcP(O)(DMCDA)SnPh3 ((R,R,RP)-2 and (S,S,SP)-2) in a diastereoselective ratio of 88:12. The absolute configuration of the major diastereomer was confirmed by single-crystal X-ray diffraction analysis. DFT calculations revealed that kinetic effects of the lithiation step cause the high diastereoselectivity of the formation of (R,R,RP)-2. Further functionalization of (R,R,RP)-2 with elemental iodine gave the enantiopure organotin iodide derivatives FcP(O)(DMCDA)SnInPh3−n ((R,R,RP)-3:, n = 1; (R,R,RP)-4, n = 2, (R,R,RP)-5, n = 3). The triorganotin fluoride FcP(O)(DMCDA)SnFPh2 ((R,R,RP)-6) was obtained by the reaction of (R,R,RP)-3 in dichloromethane with aqueous KF solution. The reaction of the compound (R,R,RP)-3 with silver triflate gave the R,R,RP-configurated triorganotin triflate FcP(O)(DMCDA)SnPh2(OTf) (7), which exists as a contact ion pair in the solid state and shows dynamic behavior in solution. The reaction of 7 with Ph3PO afforded the corresponding organotin salt [FcP(O)(DMCDA)SnPh2(OPPh3)][OTf] ((R,R,RP)8).

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Representative examples A−K8−18 for P(V)-containing ferrocene compounds with the P atom directly bound to the ferrocene moiety are shown in Chart 1. In particular, the P substituents in compounds A and D have proven their orthodirecting effect in lithiation reactions. Moreover, for these reactions diastereoselectivity was achieved either without (compound A) or by the addition of chiral auxiliaries (compound D).8,11 For many years we have been interested in inter- and intramolecularly coordinated organotin(II) and -tin(IV) compounds with one focus on derivatives containing PO→ Sn interactions.19 Such interactions are rather strong and made possible the isolation of otherwise unstable compounds such as RSnSnR20 containing Sn(I) and [R{(CO)5Cr}Sn(OPPh3)]ClO4 (R = 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2)21 containing a transition-metal-bound Sn(II) cation stabilized by both intraand intermolecular PO→Sn coordination. In a continuation of these efforts and with the intention to bring chirality into play, we report here the first results on the synthesis and structure of organotin-substituted derivatives of the chiral ferrocenyl phosphonic acid amide L (Chart 1). We

INTRODUCTION

Ferrocene is among the most spectacular organometallic compounds ever reported.1 It satisfied academic curiosity, had great impact on the understanding of chemical bonding, and last but not least paved the way to many practical applications.2−4 One important property of substituted ferrocenes is their planar chirality, which makes these compounds attractive candidates for the design of tailor-made catalysts for enantioand diastereoselective chemical reactions.2,5 Among such compounds, 1,2-disubstituted derivatives are rather prominent. Usually, they are prepared from a monosubstituted ferrocene via an intramolecularly donor group directed ortho-lithiation.6 Classic representatives of ferrocenes containing donor groups are FcCHRNMe2 (Fc = ferrocenyl, R = H, alkyl, aryl)7a−g,p and Fc−oxazoline derivatives,7h−o for which a great variety of orthosubstituted organoelement derivatives have been reported. Another type of such ortho-directing groups contains phosphorus atoms, either as P(III) or as P(V), with all sorts of different substituents. A search of the Cambridge Crystallographic Data Base (version 5.34, November 2012) for such compounds revealed the impressive number of 1971 hits, among which 104 hits are related in each case to substituents containing PO and PS donor functions and 20 hits are related to PSe groups. © XXXX American Chemical Society

Special Issue: Ferrocene - Beauty and Function Received: May 28, 2013

A

dx.doi.org/10.1021/om4004797 | Organometallics XXXX, XXX, XXX−XXX

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Chart 1

Figure 1. Displacement ellipsoid (30% probability level) plot of the molecular unit of (R,R)-1 in the crystal. Hydrogen atoms are omitted for clarity.

show that the lithiation of the latter and subsequent treatment with triphenyltin chloride gave, in a remarkable diastereoselective excess, the corresponding tetraorganotin compound that was functionalized further to give organotin halides and even a donor-stabilized triorganotin cation.

centroid(Cp1)−centroid(Cp2)−C(8) of −2.6(2)° for (R,R)-1 and C(1)−centroid(Cp1)−centroid(Cp2)−C(6) of 2.2(2)° (S,S)-1.24 A 31P NMR spectrum of compound 1 shows a singlet at δ 41.2 that is comparable with similar P(O) resonances reported in the literature.8a,22b A 1H NMR spectrum of 1 shows four unresolved resonances (δ 4.58, 4.43, 4.34, 4.15) for the protons of the substituted Cp ring as a result of their diastereotopism. Therefore, ortho-deprotonation should provide a pair of diastereomers. The deprotonation with t-BuLi/t-BuOK of the enantiopure compound (R,R)-1 and subsequent quenching of the in situ generated organolithium compound (R,R)-1-Li with triphenyltin chloride provided a crude reaction mixture that, after aqueous workup, was investigated further. The 31P NMR of the crude product showed four resonances at δ 42.5 (signal a: integral 60, J(31P−117/119Sn = 7.1 Hz, (R,R,RP)-2), 41.4 (signal b: integral 21, (R,R)-1), 41.2 (signal c: integral 11), and 39.4 (signal d: integral 8, J(31P−117/119Sn = 6.5 Hz, tentatively assigned to (R,R,SP)-2). All attempts at isolating the products attributed to signals c and d failed. Different conditions for the synthesis of compound 2 (see Scheme 1) were explored by altering the solvent (Et2O and THF) and reaction temperature (between 0 and −78 °C). The best results in terms of yield were obtained in THF at −78 to −50 °C. The same results

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RESULTS AND DISCUSSION The reaction of in situ generated lithioferrocene and (3aR,7aR)2-chloro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-oxide22a,b gave enantiopure (3aR,7aR)-2-ferrocenyl-3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-oxide ((R,R)-1, hereinafter referred to as (R,R)-FcP(O)(DMCDA)) as an orange crystalline material (Scheme 1). The synthesis of the enantiomer (S,S)-FcP(O)(DMCDA) ((S,S)-1) was carried out analogously. Single crystals suitable for X-ray diffraction analysis of 1 were obtained by recrystallization from dichloromethane. The molecular structure of compound (R,R)-1 is shown in Figure 1, and that of the corresponding enantiomer (S,S)-1 is depicted in Figure S1 (Supporting Information). Selected interatomic distances and angles for both compounds are given in Table 1. The compounds (R,R)-1 and (S,S)-1 crystallized in the socalled Sohncke23 space group P212121. The dihedral angles C(2)−C(1)−P(1)−O(1) of −37.4(3)° for (R,R)-1 and 37.4(2)° for (S,S)-1 illustrate the relative orientation of the PO group toward the upper Cp ring in the solid state, as observed in related ferrocenyl derivatives.8b The Cp rings are nearly eclipsed, as shown by the dihedral angle C(1)− Scheme 1. Synthesis of Compounds 1 and 2a

a

(R,R)-1 gave (R,R,Rp)-2:(R,R,Sp)-2 in a 88:12 diastereomeric ratio. (S,S)-1 gave (S,S,Sp)-2:(S,S,Rp)-2 in a 88:12 diastereomeric ratio. B


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Table 1. Selected Interatomic Distances (Å), Angles (deg), and Dihedral Angles (deg) for (R,R)-1, (R,R,RP)-2a, and (R,R,RP)-2b and Their Enantiomers (S,S)-1, (S,S,SP)-2a, and (S,S,SP)-2b·0.5C4H10O (R,R)-1

(R,R,RP)-2a

(R,R,RP)-2b

(S,S,SP)-2a

(S,S,SP)-2b·0.5C4H10O

X Eq1, Eq2, Eq3 Y Eq4, Eq5, Eq6

C(31) C(1), C(21), C(41)

C(31) C(1), C(21), C(41)

C(31) C(1), C(21), C(41)

C(21) C(1), C(31), C(41) C(81) C(51), C(91), C(71)

Sn(1)−O(1) Sn(2)−O(2) Sn(1)−X Sn(1)−Eq1 Sn(1)−Eq2 Sn(1)−Eq3 Sn(2)−Y Sn(2)−Eq 4 Sn(2)−Eq5 Sn(2)−Eq6 Sn(1)−Eq1−C(2) Sn(2)−Eq4−C(52) O(1)−Sn(1)−X O(2)−Sn(2)−Y Eq1−Sn(1)−Eq2 Eq1−Sn(1)−Eq3 Eq2−Sn(1)−Eq3 X−Sn(1)−Eq1 X−Sn(1)−Eq2 X−Sn(1)−Eq3 Eq4−Sn(2)−Eq5 Eq4−Sn(2)−Eq6 Eq5−Sn(2)−Eq6 Y−Sn(2)− eq 4 Y−Sn(2)−Eq5 Y−Sn(2)−Eq6 C(2)−C(1)−P(1)−O(1) C(1)−C(2)−P(1)−O(1) C(51)−C(52)−P(2)−O(2)

2.757(5)

2.944(3)

2.748(3)

2.196(3) 2.105(7) 2.142(3) 2.161(3)

2.160(4) 2.144(4) 2.129(4) 2.165(4)

2.1931(18) 2.126(4) 2.1513(19) 2.1608(18)

125.6(5)

127.4(3)

124.3(3)

175.84(17)

170.03(12)

176.63(10)

108.5(2) 117.7(2) 118.03(18) 103.0(2) 104.07(18) 103.32(16)

110.44(16) 122.46(16) 110.86(17) 99.19(17) 108.73(16) 103.50(18)

108.45(12) 117.53(11) 118.12(10) 103.49(12) 104.09(10) 102.96(10)

2.945(3) 3.279(2) 2.171(3) 2.132(4) 2.146(4) 2.149(4) 2.159(3) 2.132(4) 2.142(4) 2.147(4) 128.1(3) 130.0(2) 169.23(10) 170.81(11) 105.72(14) 126.04(14) 113.58(15) 99.94(13) 105.95(14) 103.02(14) 110.15(13) 120.27(14) 110.15(13) 103.80(14) 109.85(14) 101.75(13)

−13.9(5)

−10.3(4)

11.5(3)

−37.4(3)

(S,S)-1

37.4(2) 15.2(3) 28.3(4)

crystallized in the Sohncke space group P212121 containing one molecule in the asymmetric unit. The pseudo polymorph (S,S,SP)-2b·0.5C4H10O crystallized in the Sohncke space group P21 containing two molecules per asymmetric unit (the differences between the two molecules are illustrated by their superposition in Figure S5, Supporting Information). In all four structures the Sn(1) atoms are [4 + 1] coordinated by C(1), C(21), C(31), C(41), and O(1), and each adopts a monocapped distorted tetrahedral environment (geometric goodness:25 (R,R,RP)-2a, ΔΣ(θ) = 34°; (R,R,RP)-2b, ΔΣ(θ) = 32°; (S,S,SP)-2a, ΔΣ(θ) = 34°; (S,S,SP)-2b·0.5C4H10O, ΔΣ(θ) = 36° (molecule A)/25° (molecule B)) with O(1) approaching the Sn(1) atom via the tetrahedral face defined by C(1), C(21), and C(41). The O(1)−Sn(1) distances of 2.757(5) Å ((R,R,R P )-2a), 2.944(3) Å ((R,R,R P )-2b), 2.748(3) Å ((S,S,SP)-2a), and 2.945(3) Å (molecule A)/ 3.279(2) Å (molecule B) ((S,S,SP)-2b·0.5C4H10O) are different. They are in the same range as those previously reported for other PO→Sn coordinated tetraorganotin compounds such as (DMCDA)P(O)NMeCH(Ph)(SnMe3) (Sn−O = 2.66 Å)26 and 2,4-bis(diethoxyphosphonyl)-1-triphenylstannylbenzene (Sn−O = 2.803(3) Å).27 The difference between the structures of the polymorphs (R,R,RP)-2a and (R,R,RP)-2b is illustrated in Figure S6 (Supporting Information).

were observed for the enantiomer (S,S)-1 and its reaction with triphenyltin chloride. Independent of the reaction conditions employed, the ratio between the diastereomers R,R,RP:R,R,SP is 88:12. After purification by column chromatography the compounds (R,R,RP)-2 and (S,S,SP)-2 were obtained as orange solids. By slow evaporation of a diethyl ether solution of (R,R,RP)-2 single crystals of the polymorph (R,R,RP)-2a were obtained. Slow evaporation of an isohexane solution of (R,R,RP)-2 gave single crystals of the polymorph (R,R,RP)-2b. The molecular structure of the polymorph (R,R,RP)-2a is shown in Figure 2 and that of the polymorph (R,R,RP)-2b in Figure S2 (Supporting Information). Single crystals of (S,S,SP)-2a were obtained analogously to (R,R,RP)-2a (for the molecular structure see Figure S3, Supporting Information). Single crystals of the diethyl ether solvate (S,S,SP)-2b·0.5C4H10O were obtained by slow evaporation of a diethyl ether/CH2Cl2 solution of (S,S,SP)-2 (for the molecular structure see Figure S4, Supporting Information). The relations between the polymorphs and their solvates are shown in Scheme S1 (Supporting Information). Structural parameters for all four compounds are given in Table 1. The compounds (R,R,RP)-2a and (S,S,SP)-2a crystallized in the rare Sohncke space group P1 containing one molecule per asymmetric unit. In contrast, the polymorph (R,R,RP)-2b C


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Scheme 2. Synthesis of Compounds 3−8

Figure 2. Displacement ellipsoid (30% probability level) plot of the molecular unit of (R,R,RP)-2a in the crystal. Hydrogen atoms are omitted for clarity.

The major difference between the structures of the organotin-free and organotin-containing compounds are the dihedral angles C(1/2)−C(2/1)−P(1)−O(1) of −37.4(3)° ((R,R)-1), −13.9(5)° ((R,R,RP)-2a), −10.3(4)° ((R,R,RP)-2b), 37.4(2)° ((S,S)-1), 11.5(3)° ((S,S,SP)-2a), and 15.2(3)° (molecule A)/28.3(4)° (molecule B) ((S,S,S P )-2b· 0.5C4H10O). These differences are the result of intramolecular PO→Sn interactions being absent in (R,R)-1 and (S,S)-1 but present in the organotin derivatives. A 31P NMR spectrum of (R,R,RP)-2 in CDCl3 revealed a single resonance at δ 42.4 (J(31P−117/119Sn = 7 Hz). The 119Sn NMR spectrum of the same sample exhibits a doublet resonance at δ −125 (J(119Sn−31P) = 7 Hz). Interestingly, the electrospray mass spectrum (hereafter referred to as ESI MS) in the positive mode of compound 2 revealed, in addition to the minor intense mass cluster m/z 722.1 ((M + H)+), a major mass cluster centered at m/z 645.1 that is assigned to (M − Ph)+, indicating the PO→Sn donorinduced labilization of the Sn−CPh bond. The reactions of the tetraorganostannane (R,R,RP)-2 with one, two, and three molar equiv of elemental iodine gave the corresponding tri-, di-, and monoorganotin iodide derivatives FcP(O)(DMCDA)SnIPh2 ((R,R,RP)-3), FcP(O)(DMCDA)SnI2Ph ((R,R,RP)-4), and FcP(O)(DMCDA)SnI3 ((R,R,RP)5), respectively, as orange or red crystalline materials that show good to moderate solubility in dichloromethane and acetone (Scheme 2). Single crystals suitable for X-ray diffraction analysis of these compounds were obtained by recrystallization from a diethyl ether/hexane mixture ((R,R,RP)-3) or from acetone ((R,R,RP)4 and (R,R,RP)-5, as its acetone solvate (R,R,RP)-5·0.5C3H6O). Their molecular structures are shown in Figures 3−5, and selected interatomic distances and angles are given in Table 2.

Figure 3. Displacement ellipsoid (30% probability level) plot of the molecular unit of (R,R,RP)-3 in the crystal. Hydrogen atoms are omitted for clarity.

Compound (R,R,RP)-3 crystallized in the Sohncke space group P21 with one molecule in the asymmetric unit, and both (R,R,RP)-4 and (R,R,RP)-5·0.5C3H6O crystallized in the Sohncke space group P212121, (R,R,RP)-5·0.5C3H6O with one molecule in the asymmetric unit. The asymmetric unit of (R,R,RP)-4 contains two crystallographically independent but rather similar molecules, one of which is depicted in Figure 4, and only this will be discussed (the minor differences between the two molecules are illustrated by their superposition in Figure S7, Supporting Information). In each of the three compounds the Sn(1) atom shows a distorted trigonalbipyramidal environment (geometric goodness ΔΣ(θ) = 66° ((R,R,RP)-3), 66° ((R,R,RP)-4), 69° ((R,R,RP)-5·0.5C3H6O)) with O(1) and I(1) occupying the axial and the C(1), C(21), C(31) ((R,R,RP)-3), C(1), C(21), I(2) ((R,R,RP)-4), and C(1), I(2), I(3) atoms ((R,R,RP)-5·0.5C3H6O) occupying the D


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character of the Sn−I bonds in the monoorganotin triiodide counterbalancing the bond lengthening in the axial position. The 31P NMR spectra in CDCl3 of (R,R,RP)-3, (R,R,RP)-4, and (R,R,R P )-5 revealed single resonances at δ 49.8 (J(31P−117/119Sn) = 52 Hz), 48.8 (J(31P−117/119Sn) = 68 Hz), and 48.6 (J(31P−117/119Sn) = 99 Hz), respectively. The 119Sn NMR spectra of (R,R,RP)-3 and (R,R,RP)-4 displayed a doublet resonance at δ −171 (J(119Sn−31P) = 53 Hz) and a broad singlet at δ −404 (ν1/2 = 170 Hz), respectively, whereas, as a result of its poor solubility, no resonance could be obtained for (R,R,RP)-5 within a reasonable measurement time. The ESI MS (positive mode) of (R,R,RP)-3 showed a major mass cluster centered at m/z 645.2 that is assigned to (M − I)+. The spectrum of the diorganotin diiodide (R,R,RP)-4 is more complex. It showed five major mass clusters centered at m/z 585.1 ((M − 2I + OH)+), 627.1 ((M − 2I + OC(O)CH3)+), 1167.2 ((2 M − 4I + O + OH)+), 1209.3 ((2 M − 4I + O + OC(O)CH3)+), and 1749.8 ((3 M − 6I + 2O + OH)+), respectively. The most intense mass cluster in the spectrum of the monoorganotin triiodide (R,R,RP)-5 was centered at m/z 1533.4. Tentatively, we assigned this mass cluster to the trinuclear tinoxo cluster M, as depicted in Figure 6. The triorganotin iodide (R,R,RP)-3 was easily converted into its corresponding triorganotin fluoride (R,R,RP)-6 by reaction with potassium fluoride, KF (Scheme 2). The molecular structure of the latter, as its acetone solvate (R,R,RP)-6·C3H6O, is shown in Figure S8 (Supporting Information), and selected interatomic distances and angles are given in Table 2. The structure of (R,R,RP)-6 strongly resembles that of the triorganotin iodide (R,R,RP)-3, to the extent that even the intramolecular PO→Sn interaction at an O(1)−Sn(1) distance of 2.3623(19) Å is rather similar to that of the latter compound (O(1)−Sn(1) 2.359(3) Å) and even shorter than that found in [2-(fluorodimethylstannyl)ethyl]diphenylphosphane oxide (2.454(3) Å).29 A 19F NMR spectrum in CDCl3 of (R,R,RP)-6 showed a single resonance at δ −197.6 flanked with well-resolved J(19F−117/119Sn) satellites of 2059/2156 Hz. The latter are in the typical range for such coupling constants.30 A 31P NMR spectrum showed a resonance at δ 50.9 (J(31P-117/119Sn) = 50 Hz), while a 119Sn NMR spectrum displayed a doublet of doublets resonance at δ −217 (1J(119Sn−19F) = 2155 Hz, J(119Sn−31P) = 51 Hz). The results confirm that both the Sn−F bond and the PO→Sn coordination are retained in solution on the corresponding NMR time scales. The reaction of the compound (R,R,RP)-3 with silver triflate, AgOTf, gave the corresponding triorganotin triflate FcP(O)(DMCDA)SnPh2(OTf) ((R,R,RP)-7) as an orange crystalline material (Scheme 2). The compound (R,R,RP)-7 crystallized from acetonitrile in the Sohncke space group P21 as its acetonitrile solvate, (R,R,RP)-7·0.5CH3CN. The unit cell contains two crystallographically independent molecules, one of which is depicted in Figure 7, and only this will be discussed (the most striking difference between the two molecules is the orientation of the triflate anion, as is illustrated by their superposition in Figure S9, Supporting Information). Selected interatomic distances and angles for both molecules are given in Table 2. The Sn(1) atom is five-coordinated and exhibits a distorted trigonal-bipyramidal environment (geometric goodness of ΔΣ(θ) = 81°) with O(1) and O(11) in the axial and C(1), C(21), and C(31) in the equatorial positions. The intramolecular coordination PO→Sn at a O(1)−Sn(1) distance

Figure 4. Displacement ellipsoid (30% probability level) plot of one (out of two) molecular unit of (R,R,RP)-4 in the crystal. Hydrogen atoms and the solvate molecule are omitted for clarity.

Figure 5. Displacement ellipsoid (30% probability level) plot of the molecular unit of (R,R,RP)-5·0.5C3H6O in the crystal. Hydrogen atoms, the solvate molecule, and the second part of the disordered nonsubstituted Cp ring are omitted for clarity.

equatorial positions. As expected, the O(1)−Sn(1) distances of 2.359(3) Å ((R,R,RP)-3), 2.320(3) Å ((R,R,RP)-4), and 2.240(5) Å ((R,R,RP)-5·0.5C3H6O) decrease with increasing iodine substitution and reflect the enhanced Lewis acidity of the tin atom in the latter compound. As a result of the intramolecular PO→Sn interaction, the Sn(1)−I(1) distances of 2.8425(6) Å ((R,R,RP)-3), 2.8073(6) Å ((R,R,RP)-4), and 2.7927(7) Å ((R,R,RP)-5·0.5C3H6O) are longer than the sum of the covalent radii (2.73 Å) of tin and iodine.28 Interestingly, the effect is least pronounced for the last compound and might be a hint to the increasing ionic E


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Table 2. Selected Interatomic Distances (Å), Angles (deg), and Dihedral Angles (deg) for the R,R,RP-Configured compounds 3, 4, 5·0.5C3H6O, 6·C3H6O, 7·0.5C2H3N, and 8

a

3

4

5·0.5C3H6O

6·C3H6O

7·0.5C2H3N

8

X Eq1, Eq2, Eq3a Y Eq4, Eq5, Eq6a

I(1) C(1), C(21), C(31)

I(1) C(1), I(2), C(21) I(3) C(31), I(4), C(51)

I(1) C(1), I(2), I(3)

F(1) C(1), C(21), C(31)

O(11) C(1), C(21), C(31) O(21) C(41), C(61), C(71)

O(2) C(1), C(21), C(31)

Sn(1)−O(1) Sn(2)−O(2) Sn(1)−X Sn(1)−Eq1 Sn(1)−Eq2 Sn(1)−Eq3 Sn(2)−Y Sn(2)−Eq4 Sn(2)−Eq5 Sn(2)−Eq6 Sn(1)−Eq1−C(2) Sn(2)−Eq4−C(32) Sn(2)−Eq4−C(42) O(1)−Sn(1)−X O(2)−Sn(2)−Y Eq1−Sn(1)−Eq2 Eq1−Sn(1)−Eq3 Eq2−Sn(1)−Eq3 X−Sn(1)−Eq1 X−Sn(1)−Eq2 X−Sn(1)−Eq3 Eq4−Sn(2)−Eq5 Eq4−Sn(2)−Eq6 Eq5−Sn(2)−Eq6 Y−Sn(2)−Eq4 Y−Sn(2)−Eq5 Y−Sn(2)−Eq6 C(1)−C(2)−P(1)−O(1) C(31)−C(32)−P(2)−O(2) C(41)−C(42)−P(2)−O(2)

2.359(3)

2.320(3) 2.343(3) 2.8073(6) 2.118(5) 2.7138(5) 2.142(5) 2.8112(6) 2.096(6) 2.7058(6) 2.120(5) 118.4(4) 120.5(4)

2.240(5)

2.3623(19)

2.2491(19)

2.7927(7) 2.091(7) 2.6962(7) 2.6876(7)

2.0145(18) 2.119(3) 2.129(3) 2.133(3)

118.9(5)

118.8(2)

2.204(3) 2.207(4) 2.305(4) 2.119(5) 2.118(5) 2.116(5) 2.270(3) 2.108(5) 2.138(5) 2.133(5) 114.3(3)

171.30(10) 172.30(9) 117.07(15) 125.4(2) 113.56(15) 94.13(15) 94.348(17) 101.16(16) 114.93(15) 129.1(2) 111.77(15) 94.39(16) 96.987(18) 99.16(15) −15.8(5) −6.1(5)

176.15(13)

172.54(8)

117.15(18) 124.99(18) 114.68(3) 97.0(2) 96.18(2) 94.63(2)

117.64(11) 123.32(11) 117.34(12) 93.84(10) 95.01(11) 94.20(10)

−9.6(6)

−13.0(3)

2.8425(6) 2.120(6) 2.128(5) 2.152(6)

118.8(4)

170.77(9) 109.9(2) 128.5(2) 117.8(2) 94.08(16) 101.02(15) 94.87(17)

−10.5(5)

115.8(4) 175.37(15) 170.04(14) 118.27(19) 126.18(19) 114.85(19) 94.57(17) 92.55(19) 91.18(18) 119.63(18) 126.3(2) 114.02(19) 89.92(18) 93.70(17) 89.68(16) −9.3(5)

2.208(2) 2.115(3) 2.133(3) 2.136(3)

117.0(2)

170.12(8) 114.86(12) 129.84(13) 115.14(13) 90.61(10) 91.20(10) 92.14(11)

−7.3(3)

−5.2(5)

Eq1−Eq6 refer to the atoms located in the equatorial positions of the corresponding trigonal-bipyramidal environments.

A 31P NMR spectrum in CD2Cl2 of the triorganotin triflate (R,R,R P )-7 showed a sharp resonance at δ 55.7 (J(31P−117/119Sn) = 68 Hz). A 119Sn NMR spectrum of the same solution displayed a sharp doublet resonance at δ −183 (J(119Sn−31P) = 68 Hz). The 31P and 119Sn NMR spectra in CD3CN revealed broad resonances (δ 31P 56.0 (ν1/2 = 8 Hz, J(31P−117/119Sn) = 68); δ 119Sn −178 (ν1/2 = 340 Hz)), indicating dynamic behavior of (R,R,RP)-7 in this donor solvent. The reaction of compound (R,R,RP)-7 with triphenylphosphane oxide, Ph3PO, in CH2Cl2 provided the corresponding donor-stabilized triorganotin(IV) triflate salt (R,R,RP)-8 as an orange crystalline material (Scheme 2). Its molecular structure is shown in Figure 8, and selected interatomic distances and angles are given in Table 2. Compound (R,R,RP)-8 crystallized in the Sohncke space group P212121 with one molecule per asymmetric unit. It consists of a Ph3PO-coordinated triorganotin cation and a triflate anion being separated at distances between 5.97 Å (Sn1−F12) and 7.19 Å (Sn1−O12). The Sn(1) atom is pentacoordinated and shows an almost perfect trigonalbipyramidal environment (geometric goodness ΔΣ(θ) = 86°)

of 2.204(3) Å is rather strong and is among the shortest of such distances. The triflate anion coordinates the tin atom at a O(11)−Sn(1) distance of 2.305(4) Å. This distance is similar to that in other ferrocenylstannyl triflates (2.1392(15), 2.340(8) Å).31 An interesting aspect for the structures of 2−7·0.5CH3CN in comparison to that of 1 is that the C(1)−C(2)−P(1)−O(1) torsion angles (absolute values) ranging between −5.2(5)° ((R,R,RP)-7·0.5CH3CN) and 28.3(4)° (molecule B in (S,S,SP)2b·0.5C4H10O) for the former group of compounds are much smaller than the corresponding C(2)−C(1)−P(1)−O(1) torsion angles in (R,R)-1 (−37.4(3)°) and (S,S)-1 (37.4(2)°). Furthermore, the Sn(1)−C(1)−C(2) angles decrease in the sequence (S,S,SP)-2b·0.5C4H10O (130.0(2)°, molecule B; 128.1(3)°, molecule A) > (R,R,RP )-2b (127.4(3)°) > (R,R,R P )-2a (125.6(5)°) > (S,S,S P )-2a (124.3(3)°) > (R,R,RP)-4 (120.5(3)°, molecule B) > (R,R,RP)-5·0.5C3H6O (118.9(5)°) > (R,R,RP)-3 (118.8(4)°) > (R,R,RP)-6·C3H6O (118.8(2)°) > (R,R,RP)-4 (118.4(3)°, molecule A) > (R,R,RP)7·0.5CH3CN (115.8(4)°, molecule B) > (R,R,RP)-7·0.5CH3CN (114.3(3)°, molecule A), reflecting the increasing PO→Sn coordination. F


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Figure 8. Displacement ellipsoid (30% probability level) plot of one ion pair of (R,R,RP)-8 in the crystal. Hydrogen atoms are omitted for clarity.

Pr)2}2C6H2(Ph3PO)SnCr(CO)5][ClO4] the Ph3PO→Sn coordination is even stronger at a Sn(1)−O(3) distance of 2.1038(19) Å.21 In (R,R,RP)-8, the P(1)−O(1) (1.512(2) Å) and P(2)−O(2) (1.510(2) Å) distances are almost equal but the P(1)−O(1)−Sn(1) (120.11(12)°) and P(2)−O(2)−Sn(1) (169.33(15)°) angles differ considerably. The latter angle is even bigger than the P(3)−O(3)−Sn(1) angle of 166.80(14)° in the transition-metal complex mentioned above.21 In the simple complexes R3SnCl(OPPh3) the Sn−O distances vary between 2.2798(14) Å (R = PhCH2)32a and 2.391(4) Å (R = Ph)32b and the P−O−Sn angles fall in the range between 164.27(10) (R = PhCH2)32a and 147.4(3)° (R = Me).32c The 31P NMR spectrum of (R,R,RP)-8 in CD2Cl2 showed four resonances at δ 55.7 (J(31P−117/119Sn) = 67 Hz, (R,R,RP)7), 54.1 (J(31P−117/119Sn) = 66/69 Hz, P(O)DMCDA of (R,R,RP)-8), 41.9 (2J(31P−117/119Sn) = 143/149 Hz, Ph3PO of (R,R,RP)-8), and 28.8 (for noncoordinating Ph3PO), indicating the equilibrium (R,R,RP)-7 + Ph3PO ⇌ (R,R,RP)-8 to be slow on the 31P NMR time scale at room temperature. In CD3CN solution, the equilibrium completely shifts to the right and only the two 31P resonances for (R,R,RP)-8 were observed (δ 54.3, J(31P−117/119Sn) = 67 Hz; δ 41.5, 2J(31P−117/119Sn) = 145/150 Hz). The 119Sn NMR in CD3CN revealed a sharp doublet of doublets at δ −197 (J(119Sn−31P) = 69 Hz, 2J(119Sn−31P) = 151 Hz). The kinetic inertness at ambient temperature of the Ph3PO→Sn coordination in (R,R,RP)-8 is somewhat surprising, as related Ph3PO-stabilized organotin(IV) cations show kinetic lability.21,33 DFT Calculations. DFT calculations (at the B3LYP/ DGDZPV//B3LYP/LANL2DZ//B3LYP/3-21G level of theory) reveal (R,R,RP)-2a and its (R,R,SP)-2a diastereomer (not isolated but detected by 31P and 119Sn NMR spectroscopy) having almost the same energy (for details see the Supporting Information). Consequently, the diastereoselective formation in favor of (R,R,RP)-2a rather likely originates from kinetic effects of the initial lithiation reaction. The schematic energy diagram (Figure 9) illustrating two forms of (R,R)-1 and the

Figure 6. ESI-MS mass cluster of M (C54H72Fe3N6O7P3Sn3+): (left) measured; (right) simulated.

Figure 7. Displacement ellipsoid (30% probability level) plot of one (out of two) molecule of (R,R,RP)-7·0.5C2H3N in the crystal. Hydrogen atoms and the solvate molecule are omitted for clarity.

with the O(1) and O(2) atoms occupying the axial and the C(1), C(21), and C(31) atoms occupying the equatorial positions. The O(1)−Sn(1)−O(2) angle is 170.12(8)° and deviates only slightly from 180°. Most remarkably, the Sn(1)− O(1) distance of 2.2491(19) Å is longer than the Sn(1)−O(2) distance of 2.208(2) Å, reflecting the superior donor capacity of intermolecularly coordinating Ph3PO versus the intramolecularly coordinating CCpN2PO moiety. In the transition-metal organostannylene comp lex [4- t-Bu-2,6-{P(O)(OiG


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lithiation of the second ortho position, which presumes an earlier transition state of the former reaction path. Since the rotation barrier separating pro-R and pro-S forms is only 3.09 kcal/mol (corresponding to a first-order rate constant at the diffusion limit), the situation on the whole appertains to the Curtin−Hammett scheme with two starting forms existing in fast equilibrium whose follow-up reaction rates are determined by the corresponding activation barriers.

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CONCLUSION Starting from the enantiopure ferrocenylphosphonic diamide derivative (R,R)-1 (or (S,S)-1) the corresponding organotin derivative (R,R,RP)-2 (or (S,S,SP)-2) was obtained in high diastereoselective yield by lithiation with t-BuLi/KO-t-Bu and subsequent reaction with Ph3SnCl. As supported by DFT calculations, the latter originates from a kinetically controlled diastereoselective lithiation reaction. The tetraorganotin derivative (R,R,RP)-2 was easily converted into a variety of organotin halides (R,R,RP)-3−(R,R,RP)-6 and the triflate (R,R,RP)-7. The triflate anion in (R,R,RP)-7 is displaced by addition of triphenylphosphine oxide to give the compound (R,R,RP)-8 containing a donor-stabilized triorganostannylium cation. As a result of its chirality, the latter holds potential as a catalyst for stereoselective transformations in organic syntheses. Notably, in the ESI MS of the organotin triiodide (R,R,RP)-5 a mass cluster was detected that corresponds to a trinuclear tinoxo cluster cation that might be an attractive target to be synthesized.

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Figure 9. pro-R and pro-S configurations of (R,R)-1 and the reaction pathways with two enantiomeric ferrocenyl lithium intermediates. Dihedral atoms are numbered as in Figure 2. Only the N atoms of the benzodiazaphosphole unit are shown.

EXPERIMENTAL SECTION

General Methods. Where necessary, reactions were carried out under an inert Ar atmosphere using standard Schlenk techniques. The solvents were dried by standard methods and freshly distilled before use. The NMR experiments were carried out on a Bruker DRX 500, Bruker DRX 400, Bruker DPX 300, or Varian Mercury 200 spectrometer. NMR experiments were carried out at ambient temperature. Chemical shifts (δ) are given in ppm and are referenced to the solvent peaks with the usual values calibrated against tetramethylsilane (1H, 13C), CFCl3 (19F), and tetramethylstannane (119Sn). Elemental analyses were performed on a LECO-CHNS-932 analyzer or on a Vario Micro Cube (elementar). All compounds were dried in vacuo (0.01 mmHg) prior to analyses. The electrospray mass spectra were recorded on a Thermoquest-Finnigan instrument using CH3CN or CH2Cl2 as a mobile phase. All S,S isomers were prepared according to the synthesis described below for the R,R isomer. NMR data of these enantiomers are indistinguishable; therefore, they are not listed separately. (3aR,7aR)-2-Ferrocenyl-3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-Oxide (1). To a solution of ferrocene (6.85 g, 36.8 mmol) in THF (100 mL) was added potassium tert-butoxide (0.2 equiv). After the mixture had been cooled to −78 °C, t-BuLi (1.1 equiv, 1.9 M in pentane) was added dropwise followed by stirring of the mixture for 2 h at −50 °C to give a suspension of ferrocenyl lithium. To a suspension of (3aR,7aR)-2-chloro-1,3dimethyl-1,3,2-benzodiazaphosphole 2-oxide (8.20 g, 36.8 mmol) in THF (50 mL) that had been cooled to −78 °C was slowly added the suspension of ferrocenyl lithium via cannula. The reaction mixture was warmed to ambient temperature over a period of 12 h. After the solvent had been removed in vacuo, the residue was hydrolyzed with 1 M NaOH solution. This aqueous mixture was extracted two times with dichloromethane. The combined extracts were dried over MgSO4, and the latter was separated by filtration. The solvent of the filtrate was evaporated in vacuo. Purification of the residue by column chromatography (SiO2; 1/1 THF/CH2Cl2) gave 8.51 g (62%) of 1 as an orange solid with mp 138 °C.

intermediate ferrocenyl lithium compounds helps to rationalize the observed stereochemical outcome of the reaction sequence. The pro-R configuration of (R,R)-1 (Figure 9) has been identified as a global minimum (though the pro-S form, a local minimum, is only 1.62 kcal/mol higher in energy) separated from the pro-S form by a 3.09 kcal/mol barrier of rotation about the C(2)−P(1) bond. This barrier is lower (1.47 kcal/ mol) for the side of pro-S for the rotation via an O−Fe eclipsed configuration and higher (6.42 kcal/mol) for the counterclockwise rotation of a PO group about the Cp ring. Note that in the ferrocenyl lithium intermediates one of the two N atoms participates in coordination with Li: in the case of lithiation of the P-substituted Cp ring from the opposite side (Figure 9), it is the N···Li interaction that stabilizes the intermediate instead of a PO···Li coordination, albeit to a lesser extent. Due to the R chirality of the C(11) and C(12) atoms to which the N atoms are attached, the lone pair of N(1) is directed outward with respect to the ferrocenyl moiety, which reduces the electrostatic potential around C(1), thus favoring the lithiation of this site. The energies of the two enantiomeric ferrocenyl lithium intermediates differ by only 0.95 kcal/mol; therefore, the initial orientation of the PO group in (R,R)-1 creating preferential conditions for Li complexation in a pro-R configuration seems to be the key factor in the selectivity of lithiation and of ensuing diastereoselective introduction of the triphenylstannyl moiety to the ferrocene. In fact, lithiation of the pro-R ferrocenylphosphonic diamide (R,R)-1, leading to the R,R,RP product, has 13.58 kcal/mol greater driving force (Figure 9) than the H


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1 H NMR (499.8 MHz, CDCl3): δ 4.58 (unresolved, 1H, m-Cp), 4.43 (unresolved, 1H, m-Cp), 4.34 (unresolved, 1H, o-Cp), 4.33 (s, 5H, Cp), 4.15 (unresolved, 1H, o-Cp), 2.81 (m, 1H, NCH), 2.80 (d, 3H, NCH3, 3J(1H−31P) = 11.3 Hz), 2.25 (m, 1H, NCH), 2.20 (d, 3H, NCH3, 3J(1H−31P) = 11.6 Hz), 2.09 (m, 1H, CHCH2), 1.89 (m, 1H, CHCH2), 1.83 (m, 2H, CH2CH2), 1.36 (m, 1H, CHCH2), 1.26 (m, 2H, CH2CH2), 1.14 (m, 1H, CHCH2). 13C{1H} NMR (125.7 MHz, CDCl3): δ 72.2 (d, Cm, 3J(13C−31P) = 14.4 Hz), 71.5 (d, Cm, 3 13 J( C−31P) = 12.0 Hz), 70.5 (d, Co, 2J(13C−31P) = 9.1 Hz), 70.5 (d, Ci, 1J(13C−31P) = 171.3 Hz), 70.4 (d, Co, 2J(13C−31P) = 10.1 Hz), 69.3 (s, 5C, Cp), 64.7 (d, NCHCH2, J(13C−31P) = 6.2 Hz), 63.4 (d, NCHCH2, J(13C−31P) = 7.7 Hz), 30.1 (d, NCH3, 2J(13C−31P) = 2.4 Hz), 29.1 (d, NCH3, 2J(13C−31P) = 6.3 Hz), 29.0 (s, CHCH2CH2), 27.9 (d, CHCH 2 CH 2 , J( 1 3 C− 3 1 P) = 9.1 Hz), 24.3 (d, CH2CH2CH2CH2, J(13C−31P) = 12.9 Hz). 31P{1H} NMR (121.5 MHz, CDCl3): δ 41.2. ESI-MS (positive mode): m/z 373.1 [1 + H]+, 745.2 [2·1 + H]+. Anal. Calcd for C18H25FeN2OP (372.22): C, 58.08; H, 6.77; N, 7.53. Found: C, 57.8; H, 6.8; N, 7.4. (3aR,7aR)-[(RFc)-2-(Triphenylstannyl)ferrocenyl]3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-Oxide (2). To a solution of 1 (1.00 g, 2.9 mmol) in THF (120 mL) was added potassium tert-butoxide (0.2 equiv). After the mixture had been cooled to −78 °C, t-BuLi (1.1 equiv, 1.9 M in pentane) was added dropwise. The mixture was stirred at −50 °C for 2 h. After the mixture had been cooled to −78 °C, triphenyltin chloride (0.93 g, 2.4 mmol) was added and the reaction mixture was warmed to ambient temperature over a period of 12 h. After the solvent had been removed in vacuo, the residue was hydrolyzed with 1 M NaOH solution. This aqueous mixture was extracted two times with dichloromethane. The combined organic layers were dried over MgSO4, and the latter was removed by filtration. The solvent of the filtrate was evaporated in vacuo. Purification by column chromatography (SiO2; 1/1 THF/ CH2Cl2) provided 1.10 g (57%) of 2 as an orange solid with mp 180 °C. 1 H NMR (400.1 MHz, CDCl 3 ): δ 7.88 (m, 6H, o-Ph, 3 1 J( H−117/119Sn) = 49.0 Hz), 7.38 (m, 9H, m/p-Ph), 4.59 (unresolved, 1H, m-Cp), 4.51 (unresolved, 1H, m-Cp), 4.32 (unresolved, 1H, o-Cp), 4.15 (s, 5H, Cp), 2.81 (d, 3H, NCH3, 3J(1H−31P) = 11.5 Hz), 2.74 (m, 1H, NCH), 2.30 (m, 1H, NCH), 2.10 (m, 1H, CH2), 1.83 (m, 1 + 2H, CH2), 1.63 (d, 3H, NCH3, 3J(1H−31P) = 11.5 Hz), 1.23 (m, 1 + 2 + 1H, CH2). 13C{1H} NMR (50.3 MHz, CDCl3): δ 141.1 (s, Ci, 1 13 J( C−117/119Sn) = 564/539 Hz), 137.7 (s, Co, 2J(13C−117/119Sn) = 38 Hz), 128.2 (s, Cp, J(13C−117/119Sn) = 12 Hz), 127.9 (s, Cm, 3 13 J( C−117/119Sn) = 52 Hz), 79.1 (d, Cp-CSn, 2J(13C−31P) = 14.6 Hz), 75.8 (d, CP, 1J(13C−31P) = 174.2 Hz), 75.0 (d, Cp-CHCHCH, 3 13 J( C−31P) = 18.4 Hz), 74.4 (d, Cp-CHCP, 2J(13C−31P) = 11.5 Hz), 71.5 (d, Cp-CHCSn, 3J(13C−31P) = 16.1 Hz), 69.4 (s, 5C, Cp), 65.1 (d, NCHCH2, J(13C−31P) = 6.1 Hz), 63.4 (d, NCHCH2, J(13C−31P) = 7.7 Hz), 30.6 (d, NCH3, 2J(13C−31P) = 1.5 Hz), 29.3 (d, CHCH2CH2, J(13C−31P) = 10.0 Hz), 28.0 (d, CHCH2CH2, J(13C−31P) = 8.4 Hz), 27.8 (d, NCH3, J(13C−31P) = 4.6 Hz), 24.3 (d, CH2CH2CH2CH2, J(13C−31P) = 6.1 Hz). 31P{1H} NMR (121.5 MHz, CDCl3): δ 42.4 (J(31P−117/119Sn) = 7 Hz). 119Sn{1H} NMR (111.9 MHz, CDCl3): δ −125 (d, J(119Sn−31P) = 7 Hz). ESI-MS (positive mode): m/z 645.1 [2 − Ph]+, 722.1 [2]+, 1462.9 [2·2 + H3O]+. Anal. Calcd for C36H39FeN2OPSn (721.24): C, 59.95; H, 5.45; N, 3.88. Found: C, 59.8; H, 5.4; N, 3.9. (3aR,7aR)-[(R F c )-2-(Iododiphenylstannyl)ferrocenyl]3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-Oxide (3). To an ice-cooled solution of 2 (0.50 g, 0.7 mmol) in CH2Cl2 (20 mL) was added in small portions 1 molar equiv of elemental iodine (0.18 g, 0.7 mmol). The reaction mixture was warmed to ambient temperature. The solvent was removed in vacuo, and 0.53 g (99%) of 3 remained as an orange solid with mp 230 °C. 1 H NMR (300.1 MHz, CDCl3): δ 8.49 (d, 2H, o-Ph, 3J(1H−1H) = 6.9 Hz, 3J(1H−117/119Sn) = 74 Hz), 7.96 (d, 2H, o-Ph, 3J(1H−1H) = 7.7 Hz, 3J(1H−117/119Sn) = 69 Hz), 7.20−7.57 (complex pattern, 6H, m/p-Ph), 5.22 (unresolved, 1H, Cp), 4.77 (unresolved, 1H, Cp), 4.41 (unresolved, 1H, Cp), 4.18 (s, 5H, Cp), 2.85 (m, 1H, NCH), 2.69 (d, 3H, NCH3, 3J(1H−31P) = 12.1 Hz), 2.47 (m, 1H, NCH), 2.12 (m, 1H,

CHCH2CH2), 1.89 (d, 3H, NCH3, 3J(1H−31P) = 12.1 Hz), 1.79−1.97 (m, 3H, CHCH 2 CH 2 ), 1.13−1.46 (complex pattern, 4H, CHCH2CH2). 13C{1H} NMR (100.6 MHz, CDCl3): δ 143.7 (d, Ci, J(13C−31P) = 1.9 Hz), 140.5 (d, Ci, J(13C−31P) = 1.9 Hz), 137.3 (s, Co, 2 13 J( C−117/119Sn) = 55.4 Hz), 135.8 (s, Co, 2J(13C−117/119Sn) = 52.5 Hz), 129.1 (s, Cp, 4J(13C−117/119Sn) = 16.5 Hz), 128.6 (s, Cp, 4 13 J( C−117/119Sn) = 14.6 Hz), 127.9 (s, Cm, 3J(13C−117/119Sn) = 73.9 Hz), 84.0 (d, Cp-CSn, 2J(13C−31P) = 18.5 Hz), 79.1 (d, CpCHCHCH, 3J(13C−31P) = 14.6 Hz), 76.2 (d, Cp-CHCP, 2J(13C−31P) = 12.6 Hz), 71.4 (d, CP, 1J(13C−31P) = 173.9 Hz), 70.0 (d, CpCHCSn, 3J(13C−31P) = 15.6 Hz), 69.6 (s, 5C, Cp), 64.8 (d, NCHCH2, J(13C−31P) = 5.8 Hz), 63.7 (d, NCHCH2, J(13C−31P) = 8.8 Hz), 30.2 (d, NCH3, 2J(13C−31P) = 1.9 Hz), 28.7 (d, CHCH2CH2, J(13C−31P) = 10.7 Hz), 28.2 (d, NCH3, 2J(13C−31P) = 4.9 Hz), 27.8 (d, CHCH2CH2, J(13C−31P) = 8.8 Hz), 24.0 (d, CH2CH2CH2CH2, J(13C−31P) = 19.4 Hz). 31P{1H} NMR (121.5 MHz, CDCl3): δ 49.8 (J(31P−117/119Sn) = 52 Hz). 119Sn{1H} NMR (111.9 MHz, CDCl3): δ −171 (d, J(119Sn−31P) = 53 Hz). ESI-MS (positive mode): m/z 645.2 [3 − I]+. ESI-MS (negative mode): m/z 127.0 [I]−. Anal. Calcd for C30H34FeIN2OPSn (771.04): C, 46.73; H, 4.44; N, 3.63. Found: C, 46.4; H, 4.5; N, 3.6. (3aR,7aR)-[(R F c )-2-(Diiodophenylstannyl)ferrocenyl]3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-Oxide (4). Compound 4 was obtained according to the procedure given for synthesis of compound 3 (0.83 g, 1.2 mmol of 2) by using 2 molar equiv of elemental iodine (0.61 g, 2.4 mmol) instead of 1 molar equiv. The solvent was removed in vacuo, giving 0.92 g (97%) of 4 as a red solid with mp 220 °C. 1 H NMR (499.8 MHz, CDCl3): δ 8.22 (d, 2H, o-Ph, 3J(1H−1H) = 7 Hz, 3J(1H−117/119Sn) = 98 Hz), 7.45 (t, 2H, m-Ph, 3J(1H−1H) = 7 Hz), 7.37 (t, 1H, p-Ph, 3J(1H−1H) = 7 Hz), 5.08 (m, 1H, Cp), 4.81 (m, 1H, Cp), 4.47 (m, 1H, Cp), 4.26 (s, 5H, Cp), 2.85 (m, 1H, NCH), 2.72 (d, 3H, NCH3, 3J(1H−31P) = 12.2 Hz), 2.50 (m, 1H, NCH), 2.20 (d, 3H, NCH3, 3J(1H−31P) = 12.2 Hz), 2.11 (m, 1H, CHCH2CH2), 1.97 (m, 1H, CHCH2CH2), 1.87 (m, 2H, CHCH2CH2), 1.10−1.47 (complex pattern, 4H, CHCH2CH2). 13C{1H} NMR (100.6 MHz, CDCl3): δ 139.5 (d, Ci, 3/4J(13C−31P) = 2.9 Hz), 135.1 (s, Co, 2 13 J( C−117/119Sn) = 71.0 Hz), 130.1 (s, Cp, 4J(13C−117/119Sn) = 20.4 Hz), 128.2 (s, Cm, 3J(13C−117/119Sn) = 98.6 Hz), 83.0 (d, Cp-CSn, 2 13 J( C−31P) = 16.5 Hz), 77.5 (d, Cp-CHCHCH, 3J(13C−31P) = 13.6 Hz), 76.7 (d, Cp-CHCP, 2J(13C−31P) = 11.7 Hz), 71.6 (d, CP, 1 13 J( C−31P) = 172.0 Hz), 70.4 (d, Cp-CHCSn, 3J(13C−31P) = 15.6 Hz), 70.1 (s, 5C, Cp), 65.0 (d, NCHCH2, J(13C−31P) = 6.8 Hz), 63.7 (d, NCHCH2, J(13C−31P) = 8.8 Hz), 30.3 (d, NCH3, 2J(13C−31P) = 1.9 Hz), 28.8 (d, CHCH2CH2, J(13C−31P) = 10.7 Hz), 28.6 (d, NCH3, 2 13 J( C−31P) = 4.9 Hz), 27.7 (d, CHCH2CH2, J(13C−31P) = 8.7 Hz), 24.0 (d, CH2CH2CH2CH2, J(13C−31P) = 18.5 Hz). 31P{1H} NMR (81.0 MHz, CDCl3): δ 48.9 (J(31P−117/119Sn) = 68 Hz). 119Sn{1H} NMR (111.9 MHz, CDCl3): δ −404 (υ1/2 = 190 Hz). ESI-MS (positive mode): m/z 585.1 [(4 − 2I + OH)+], 627.1 [(4 − 2I + OC(O)CH3)+], 1167.2 [(2·4 − 4I + O + OH)+], 1209.3 [(2·4 − 4I + O + OC(O)CH3)+], 1749.8 [(3·4 − 6I + 2O + OH)+], 1791.6 [(3·4 − 6I + 2O + OC(O)CH3)+]. ESI-MS (negative mode): m/z 127.0 [I]−. Anal. Calcd for C24H29FeI2N2OPSn (820.84): C, 35.12; H, 3.56; N, 3.41. Found: C, 35.4; H, 3.5; N, 3.4. (3aR,7aR)-[(RFc)-2-(Triiodostannyl)ferrocenyl]-3a,4,5,6,7,7aoctahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-Oxide (5). Compound 5 was obtained according to the procedure given for synthesis of compound 3 (0.54 g, 0.7 mmol of 2) using 3 molar equiv of elemental iodine (0.53 g, 2.1 mmol) instead of 1 molar equiv. The solvent was removed in vacuo, giving 0.62 g (95%) of 5 as a red solid with mp 276 °C dec. 1 H NMR (400.1 MHz, CDCl3): δ 4.95 (unresolved, 1H, Cp), 4.83 (unresolved, 1H, Cp), 4.59 (s, 5H, Cp), 4.49 (unresolved, 1H, Cp), 2.84 (d, 3H, NCH3, 3J(1H−31P) = 12.5 Hz), 2.82 (m, 1H, NCH), 2.52 (m, 1H, NCH), 2.19 (d, 3H, NCH3, 3J(1H−31P) = 14.0 Hz), 2.17 (m, 2H, CHCH2CH2), 1.98 (m, 1H, CHCH2CH2), 1.89 (m, 2H, CHCH2CH2), 1.20−1.45 (complex pattern, 3H, CHCH2CH2). 31 1 P{ H} NMR (81.0 MHz, CDCl3): δ 48.6 (J(31P−117/119Sn) = 99 Hz). ESI-MS (positive mode): m/z 1533.4 [(3·5 − 9I + 4O)+]; 1595.9 I


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(not assigned). ESI-MS (negative mode): m/z 127.0 [I]−, 380.8 [I3]−. Anal. Calcd for C18H24FeI3N2OPSn (870.64): C, 24.83; H, 2.78; N, 3.22. Found: C, 25.3; H, 2.8; N, 2.9. (3aR,7aR)-[(R Fc )-2-(Fluorodiphenylstannyl)ferrocenyl]3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-Oxide (6). To a solution of 3 (0.13 g, 0.17 mmol) in CH2Cl2 (20 mL) an aqueous solution of potassium fluoride was added.The biphasic system was stirred for 72 h. The organic phase was separated, washed with water, and dried over MgSO4. After the MgSO4 had been separated by filtration, the solvent of the filtrate was removed in vacuo, giving 0.93 g (83%) of 6 as orange solid with mp 219 °C. 1 H NMR (200.1 MHz, CDCl3): δ 8.28 (dd, 2H, o-Ph, 3J(1H−1H) = 7.8 Hz, 4J(1H−1H) = 1.7 Hz, 3J(1H−117/119Sn) = 70 Hz), δ 7.94 (dd, 2H, o-Ph, 3J(1H−1H) = 7.8 Hz, 4J(1H−1H) = 1.7 Hz, 3J(1H−117/119Sn) = 70 Hz), 7.20−7.59 (complex pattern, 6H, m/p-Ph), 4.95 (unresolved, 1H, Cp), 4.74 (unresolved, 1H, Cp), 4.31 (unresolved, 1H, Cp), 4.10 (s, 5H, Cp), 2.92 (m, 1H, NCH), 2.83 (d, 3H, NCH3, 3 1 J( H−31P) = 12.0 Hz), 2.47 (m, 1H, NCH), 2.17 (m, 1H, CHCH2CH2), 1.93 (d, 3H, NCH3, 3J(1H−31P) = 12.0 Hz), 1.84− 2.02 (m, 3H, CHCH2CH2), 1.13−1.55 (complex pattern, 4H, CHCH2CH2). 13C{1H} NMR (100.6 MHz, CDCl3): δ 143.4 (dd, Ci, 2J(13C−19F) = 14.6 Hz, J(13C−31P) = 1.9 Hz), δ 143.0 (dd, Ci, 2 13 J( C−19F) = 15.0 Hz, J(13C−31P) = 1.9 Hz), 136.4 (d, Co, 3 13 J( C−19F) = 2.9 Hz, 2J(13C−117/119Sn) = 50.0 Hz), 136.0 (d, Co, 3 13 J( C−19F) = 2.4 Hz, 2J(13C−117/119Sn) = 50.1 Hz), 129.1 (s, Cp, 4 13 J( C−117/119Sn) = 15.6 Hz), 128.8 (s, Cp, 4J(13C−117/119Sn) = 14.6 Hz), 128.1 (s, Cm, 3J(13C−117/119Sn) = 73.9 Hz), 128.0 (s, Cm, 3 13 J( C−117/119Sn) = 70.3 Hz), 82.9 (dd, Cp-CSn, 2J(13C−19F) = 31.6 Hz, 2J(13C−31P) = 18.5 Hz), 77.1 (dd, Cp-CHCHCH, 4J(13C−19F) = 1.9 Hz, 3J(13C−31P) = 14.6 Hz), 76.3 (d, Cp-CHCP, 2J(13C−31P) = 12.6 Hz), 72.1 (dd, CP, 3J(13C−19F) = 4.9 Hz, 1J(13C−31P) = 173.5 Hz), 69.6 (s, 5C, Cp), 68.9 (dd, Cp-CHCSn, 3J(13C−19F) = 1.9 Hz, 3 13 J( C−31P) = 16.0 Hz), 65.0 (d, NCH3CHCH2, J(13C−31P) = 6.3 Hz), 63.9 (d, NCHCH2, J(13C−31P) = 8.8 Hz), 30.3 (d, NCH3, 2 13 J( C−31P) = 1.5 Hz), 28.9 (d, CHCH2CH2, J(13C−31P) = 10.7 Hz), 28.6 (d, NCH3, 2J(13C−31P) = 4.4 Hz), 28.0 (d, CHCH2CH2, J(13C−31P) = 8.3 Hz), 24.1 (d, CH2CH2CH2CH2, J(13C−31P) = 18.0 Hz). 19F NMR (188.3 MHz, CDCl3): δ −197.6 (1J(19F−117/119Sn) = 2059/2156 Hz). 31P{1H} NMR (81.0 MHz, CDCl3): δ 50.9 (J(31P−117/119Sn) = 50 Hz). 119Sn{1H} NMR (111.9 MHz, CDCl3): δ −217 (dd, 1J(119Sn−19F) = 2155 Hz, J(117/119Sn−31P) = 51 Hz). ESIMS (positive mode): m/z 645.1 [(6 − F)+]; 1305.4 [(2·6 − 2·F + OH)+]. Anal. Calcd for C30H34FFeN2OPSn (663.13): C, 54.34; H, 5.17; N, 4.22. Found: C, 54.4; H, 5.3; N, 4.1. (3aR,7aR)-[(R Fc )-2-(Triflatodiphenylstannyl)ferrocenyl]3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-Oxide (7). To a solution of 3 (0.42 g, 0.54 mmol) in CH2Cl2 (20 mL) a solution of silver triflate (0.14 g, 0.54 mmol) in CH3CN was added in the dark. The precipitate of AgI was separated by filtration. The solvent of the filtrate was removed in vacuo, giving 0.42 g (97%) of 7 as an orange solid. 1 H NMR (300.1 MHz, CD2Cl2): δ 8.15 (d, 2H, o-Ph, 3J(1H−1H) = 7.3 Hz, 3J(1H−117/119Sn) = 71 Hz), 7.77 (d, 2H, o-Ph, 3J(1H−1H) = 3.6 Hz, 3J(1H−117/119Sn) = 71 Hz), 7.56 (complex pattern, 3H, m/pPh), 7.41 (complex pattern, 3H, m/p-Ph), 5.35 (unresolved, 1H, oCp), 4.94 (unresolved, 1H, m-Cp), 4.54 (unresolved, 1H, m-Cp), 4.29 (s, 5H, Cp), 2.87 (m, 1H, NCH), 2.73 (d, 3H, NCH3, 3J(1H−31P) = 12.8 Hz), 2.57 (m, 1H, NCH), 2.15 (m, 1H, CHCH2CH2), 2.01 (d, 3H, NCH3, 3J(1H−31P) = 12.0 Hz), 1.86 (m, 3H, CHCH2CH2), 1.12− 1.50 (complex pattern, 4H, CHCH2CH2). 13C{1H} NMR (100.6 MHz, CD2Cl2): δ 141.9 (d, Ci, J(13C−31P) = 1.9 Hz), 140.9 (unresolved, Ci), 136.6 (s, Co, 2J(13C−117/119Sn) = 52.5 Hz), 135.9 (s, Co, 2J(13C−117/119Sn) = 52.5 Hz), 130.6 (s, Cp, 4J(13C−117/119Sn) = 15.6 Hz), 130.3 (s, Cp, 4J(13C−117/119Sn) = 14.6 Hz), 129.4 (s, Cm, 3 13 J( C−117/119Sn) = 77.8 Hz), 129.1 (s, Cm, 3J(13C−117/119Sn) = 71.9 Hz), 81.8 (d, Cp-CSn, 2J(13C−31P) = 19.4 Hz), 79.2 (d, CpCHCHCH, 3J(13C−31P) = 12.6 Hz), 78.3 (d, Cp-CHCP, 2J(13C−31P) = 14.6 Hz), 71.0 (d, CP, 1J(13C−31P) = 174.9 Hz), 70.5 (d, CpCHCSn, 3J(13C−31P) = 16.5 Hz), 70.7 (s, 5C, Cp), 65.5 (d, NCHCH2,

J(13C−31P) = 6.8 Hz), 64.7 (d, NCHCH2, J(13C−31P) = 8.8 Hz), 30.6 (d, NCH3, 2J(13C−31P) = 1.9 Hz), 29.0 (d, CHCH2CH2, J(13C−31P) = 10.7 Hz), 28.9 (d, NCH3, 2J(13C−31P) = 3.9 Hz), 28.5 (d, CHCH2CH2, J(13C−31P) = 8.8 Hz), 24.5 (d, CH2CH2CH2CH2, J(13C−31P) = 21.4 Hz). 31P{1H} NMR (121.5 MHz, CD2Cl2): δ 55.7 (J(31P−117/119Sn) = 68 Hz). 119Sn{1H} NMR (111.9 MHz, CD2Cl2): δ −183 (d, J(119Sn−31P) = 68 Hz). 1 H NMR (300.1 MHz, CD3CN): δ 8.06 (d, 2H, o-Ph, 3J(1H−1H) = 5.9 Hz, 3J(1H−117/119Sn) = 70 Hz), 7.56 (d, 2H, o-Ph, 3J(1H−1H) = 7.0 Hz, 3J(1H−117/119Sn) = 79 Hz), 7.39 (unresolved, 6H, m/p-Ph), 5.03 (unresolved, 1H, o-Cp), 4.96 (unresolved, 1H, m-Cp), 4.57 (unresolved, 1H, m-Cp), 4.17 (s, 5H, Cp), 2.80 (m, 1H, NCH), 2.74 (d, 3H, NCH3, 3J(1H−31P) = 12.4 Hz), 2.60 (m, 1H, NCH), 2.12 (m, 1H, CHCH2CH2), 1.88 (d, 3H, NCH3, 3J(1H−31P) = 12.4 Hz), 1.79 (m, 3H, CHCH 2 CH 2 ), 1.03−1.48 (complex pattern, 4H, CHCH2CH2). 13C{1H} NMR (100.6 MHz, CD3CN): δ 137.0 (s, Co, 2J(13C−117/119Sn) = 56 Hz), 136.2 (s, Co, 2J(13C−117/119Sn) = 53 Hz), 131.6 (s, Cp), 131.3 (s, Cp), 130.2 (s, Cm), 130.0 (s, Cm), 79.9 (d, Cp-CHCHCH, 3J(13C−31P) = 10.7 Hz), 78.0 (d, Cp-CHCP, 2 13 J( C−31P) = 12.6 Hz), 71.7 (d, Cp-CHCSn, 3J(13C−31P) = 15.6 Hz), 71.1 (s, 5C, Cp), 65.9 (d, NCHCH2, J(13C−31P) = 5.8 Hz), 64.9 (d, NCHCH2, J(13C−31P) = 8.8 Hz), 30.8 (s, NCH3), 29.3 (d, CHCH2CH2, J(13C−31P) = 10.7 Hz), 29.0 (d, NCH3, 2J(13C−31P) = 4.9 Hz), 28.8 (d, CHCH2CH2, J(13C−31P) = 8.8 Hz), 24.8 (d, CH2CH2CH2CH2, J(13C−31P) = 20.4 Hz). The resonances for the Ci carbon atoms were not found. The 13C NMR triflate signal is not reported. 19F NMR (282.4 MHz, CD3CN): δ −78.2. 31P{1H} NMR (121.5 MHz, CD3CN): δ 56.0 (J(31P−117/119Sn) = 68 Hz). 119Sn{1H} NMR (111.9 MHz, CD3CN): δ −178 (broad). Anal. Calcd for C31H34F3FeN2O4PSSn (793.20): C, 46.94; H, 4.32; N, 3.53. Found: C, 46.6; H, 4.6; N, 3.6. Synthesis of [FcP(O)(DMCDA)SnPh2(OPPh3)][OTf] (8). To a solution of 7 (0.29 g, 0.36 mmol) in CH2Cl2 (15 mL) was added Ph3PO (0.10 g, 0.36 mmol). The addition of isohexane caused precipitation of 8 (0.33 g, 83%) as an orange solid with mp 193 °C. 1 H NMR (400.1 MHz, CD3CN): δ 7.94 (d, 2H, o-PhSn, 3J(1H−1H) = 6.5 Hz, 3J(1H−117/119Sn) = 76/64 Hz), 7.10−7.81 (complex pattern, 23H, Ph), 4.90 (unresolved, 1H, o-Cp), 4.61 (unresolved, 1H, m-Cp), 4.58 (unresolved, 1H, m-Cp), 4.12 (s, 5H, Cp), 2.77 (m, 1H, NCH), 2.68 (d, 3H, NCH3, 3J(1H−31P) = 12.3 Hz), 2.63 (m, 1H, NCH), 2.13 (m, 1H, CHCH2CH2), 1.99 (d, 3H, NCH3, 3J(1H−31P) = 12.6 Hz), 1.82 (m, 3H, CHCH2CH2), 1.12−1.43 (complex pattern, 4H, CHCH2CH2). 13C{1H} NMR (100.6 MHz, CD3CN): δ 143.3 (d, Ci‑Sn, J(13C−31P) = 1.9 Hz), 140.1 (unresolved, Ci‑Sn), 137.2 (s, Co‑Sn, 2 13 J( C−117/119Sn) = 52.5 Hz), 135.9 (s, Co‑Sn, 2J(13C−117/119Sn) = 53.0 Hz), 135.0 (d, Cp‑P, 1J(13C−31P) = 1.9 Hz), 133.4 (d, Cm‑P, 1J(13C−31P) = 11.2 Hz), 131.3 (s, Cp‑Sn), 130.7 (s, Cp‑Sn), 130.4 (d, Co‑P, 1 13 J( C−31P) = 12.6 Hz), 129.9 (s, Cm‑Sn, 3J(13C−117/119Sn) = 76.8 Hz), 129.8 (s, Cm‑Sn, 3J(13C−117/119Sn) = 69.0 Hz), 128.4 (d, Ci‑P, 1 13 J( C−31P) = 108.4 Hz), 81.3 (d, Cp-CSn, 2J(13C−31P) = 21.4 Hz), 79.6 (d, Cp-CHCHCH, 3J(13C−31P) = 12.2 Hz), 77.9 (d, Cp-CHCP, 2 13 J( C−31P) = 13.6 Hz), 72.7 (d, CP, 1J(13C−31P) = 173.0 Hz), 71.6 (d, Cp-CHCSn, 3J(13C−31P) = 16.0 Hz), 71.0 (s, 5C, Cp), 66.0 (d, NCH3CHCH2, J(13C−31P) = 6.3 Hz), 64.8 (d, NCH3CHCH2, J(13C−31P) = 9.2 Hz), 31.0 (d, NCH3), 29.4 (d, CHCH2CH2, J(13C−31P) = 11.2 Hz), 29.2 (d, NCH3, 2J(13C−31P) = 3.9 Hz), 28.8 (d, CHCH2CH2, J(13C−31P) = 8.8 Hz), 24.8 (d, CH2CH2CH2CH2, J(13C−31P) = 20.4 Hz). The 13C NMR triflate signal is not reported. 19 F NMR (282.4 MHz, CD3CN): δ −78.4. 31P{1H} NMR (121.5 MHz, CD3CN): δ 54.3 (s, PP(O)DMCDA, J(31P−117/119Sn) = 67 Hz), 41.5 (s, PP(O)Ph3, 2J(31P−117/119Sn) = 145/150 Hz). 119Sn{1H} NMR (111.9 MHz, CD3CN): δ −197 (dd, J(119Sn−31P) = 69 Hz, 2J(119Sn−31P) = 151 Hz). 31 1 P{ H} NMR (121.5 MHz, CD2Cl2): δ 54.1 (s, PP(O)DMCDA, J(31P−117/119Sn) = 66/69 Hz), 41.9 (s, PP(O)Ph3, 2J(31P−117/119Sn) = 143/149 Hz). 119Sn{1H} NMR (111.9 MHz, CD2Cl2): δ −197 (dd, J(119Sn−31P) = 69 Hz, 2J(119Sn−31P) = 150 Hz). Due to the equilibrium of compound 8 and 7 + Ph3PO in CD2Cl2 additional J


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signals were observed in the 31P NMR (δ 55.7 (J(31P−117/119Sn) = 67 Hz) for 7 (∼11%) and 28.8 for Ph3PO (∼7%)). ESI-MS (positive mode): m/z = 645.1 [(8 − CF3SO3 − OPPh3)+]; 923.2 [(8 − CF3SO3)+]; 1305.4 [(2·8 − 2·CF3SO3 − 2·OPPh3 + OH)+];. ESI-MS (negative mode): m/z 149.1 [CF3SO3]−. No elemental analysis was performed. ESI MS. Electrospray mass spectra were recorded on a Thermoquest-Finnigan instrument using CH3CN as the mobile phase. The samples were introduced as solutions in CH3CN via a syringe pump operating at 0.5 μL/min. The capillary voltage was 4.5 kV, while the cone skimmer voltage varied between 50 and 250 kV. Identification of the expected ions was assisted by comparison of experimental and calculated isotope distribution patterns. The m/z values reported correspond to those of the most intense peak in the corresponding isotope pattern. Crystallography. All intensity data were collected with an XcaliburS CCD diffractometer (Oxford Diffraction) using Mo Kα radiation at 110 K. The structures were solved with direct methods using SHELXS-97,34 and refinements were carried out against F2 by using SHELXL-97.34 All non-hydrogen atoms were refined using anisotropic displacement parameters. The C−H hydrogen atoms were positioned with idealized geometry and refined using a riding model. In compound 5·0.5C3H6O the unsubstituted Cp ring is affected by disorder and refined with a split model over two positions. Their occupancy values were refined freely until a constant number was obtained (0.64585:0.35415), and their Uij values were restrained to nearly isotropic behavior. The solvate molecules in compounds 5· 0.5C3H6O and 6·C3H6O were found to be severely disordered and removed by Squeeze(Platon)35 to improve the main part of the structures. CCDC-941121 ((R,R)-1), CCDC-941122 ((S,S)-1), CCDC-941123 ((R,R,R P )-2a), CCDC-941124 ((R,R,R P )-2b), CCDC-941125 ((S,S,S p )-2a), CCDC-949319 ((S,S,S p )-2b· 0.5C 4 H 10 O), CCDC-941126 ((R,R,R P )-3), CCDC-941127 ((R,R,R P)-4), CCDC-941128 ((R,R,R P)-5·0.5C 3 H6 O), CCDC941129 ((R,R,R P )-6·C 3 H 6 O), CCDC-941130 ((R,R,R P )-7· 0.5C2H3N), and CCDC 950614 ((R,R,RP)-8) contain supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www. ccdc.cam.ac.uk/data_request/cif. The crystallographic data are given in the Supporting Information (Tables S−S3). For decimal rounding of numerical parameters and su values the rules of IUCr have been employed.36 Computational Details. Geometry optimization of (R,R,SP)-2′ and (R,R,RP)-2′ was performed by DFT B3LYP/DGDZVP//B3LYP/ LANL2DZ//B3LYP/3-21G calculations converging to the structures showing no negative vibration frequencies (harmonic frequency analysis using the same split valence double-ζ basis set DGDZVP37). Thermochemical data were obtained for 298.15 K and P = 1 atm on the structures containing main isotopes only. Thermal energy corrections were applied without scaling, supposing similar systematic errors of frequency calculations for each enantiomer. NBO analysis was carried out at the same level using the procedure38 implemented in Gaussian 03.39

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ACKNOWLEDGMENTS Parts of this work were first presented at the 10th International Ferrocene Colloquium, February 15−17, 2012, Braunschweig, Germany (book of abstracts O11) and at the 11th International Ferrocene Colloquium, February 6−8, 2013, Hannover, Germany (book of abstracts P09).

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REFERENCES

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ASSOCIATED CONTENT

S Supporting Information *

CIF files, Figures S1−S10, and Tables S1−S4 giving crystallographic data for 1−8 and additional DFT material. This material is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Author Contributions §

DFT calculations.

Notes

The authors declare no competing financial interest. K


Organometallics

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Diastereoselective ortho-Metalation of a Chiral Ferrocenylphosphonic

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