Monomeric Bis(η2-alkyne) Complexes of Copper ... - ACS Publications

J. Am. Chem. Soc. 1996, 118, 4817-4829

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Monomeric Bis(η2-alkyne) Complexes of Copper(I) and Silver(I) with η1-Bonded Alkyl, Vinyl, and Aryl Ligands Maurits D. Janssen,† Katrin Ko1 hler,‡ Mathias Herres,‡ Alain Dedieu,§ Wilberth J. J. Smeets,⊥ Anthony L. Spek,⊥,| David M. Grove,† Heinrich Lang,*,‡ and Gerard van Koten*,† Contribution from the Department of Metal Mediated Synthesis, Debye Institute, Utrecht UniVersity, Padualaan 8, 3584 CH Utrecht, The Netherlands, Anorganisch-Chemisches Institut, Ruprecht-Karls-UniVersita¨ t Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany, Institut le Bel, UniVersite´ Louis Pasteur, 4 Rue Blaise Pascal, 67008 Strasbourg, France, and Department of Crystal and Structural Chemistry, BijVoet Center for Biomolecular Research, Utrecht UniVersity, Padualaan 8, 3584 CH Utrecht, The Netherlands ReceiVed December 1, 1995X Abstract: Two synthetic routes to compounds [(η5-C5H4SiMe3)2Ti(CtCSiMe3)2]MR (abbreviated as [1‚MR]; M ) Cu: R ) Me (5), CH2SiMe3 (6), Et (7), nBu (8), C(H)dCH2 (9), C6H2Me3-2,4,6 (13), C6H4Me-4 (14), C6H4OMe-4 (15), C6H4NMe2-4 (16), C6H5 (17); M ) Ag: R ) C6H2Me3-2,4,6 (18)) are described. These compounds contain monomeric MR entities, which are η2-bonded by both alkyne ligands of the organometallic 3-titanio-1,4-pentadiyne [(η5-C5H4SiMe3)2Ti(CtCSiMe3)2] (1). The X-ray structures of 5, 13, and 18 have been solved. Crystals of 5 are monoclinic, space group C2/c, with a ) 19.477(1) Å, b ) 10.3622(6) Å, c ) 16.395(1) Å, β ) 95.287(5)°, V ) 3294.8(3) Å3, Z ) 4, and final R ) 0.030 for 3232 reflections with F g 4σ(F) and 240 parameters. Crystals of 13 are orthorhombic, space group Pbcn, with a ) 12.4290(9) Å, b ) 19.8770(8) Å, c ) 15.532(1) Å, V ) 3837.2(4) Å3, Z ) 4, and final R ) 0.026 for 3082 reflections with I g 2.5σ(I) and 217 parameters. The mesitylcopper compound 13 is isostructural with the mesitylsilver compound 18, and crystals of 18 are orthorhombic, space group Pbcn, with a ) 12.47(3) Å, b ) 20.00(3) Å, c ) 15.53(3) Å, V ) 3873(13) Å3, Z ) 4, and final R ) 0.055 for 2068 reflections with I g 2.5σ(I) and 188 parameters. All compounds contain a monomeric bis(η2-alkyne)M(η1-R) unit (M ) Cu or Ag) in which the group 11 metal atom is trigonally coordinated by the bis(η2-alkyne) chelate 1 and an η1-bonded monoanionic organic ligand. A bonding description of the bis(η2-alkyne)M(η1-R) entity (M ) Cu, Ag) is discussed. The alkylcopper compounds 5-8 decompose in solution either Via nucleophilic substitution of one SiMe3 group in 1 to eliminate RSiMe3 or Via β-hydride elimination (7 and 8) to eliminate the corresponding alkene, whereas arylcopper compounds 14-17, which lack ortho-substituents rearrange in solution Via addition of the monomeric arylcopper entity to one of the alkynes within [1‚CuR] to yield unstable 1,1-bimetallaalkene complexes. When R is the monoanionic terdentate ligand {C6H3(CH2NMe2)2-2,6}, the coordination complex [1‚CuR] is not isolated, while the corresponding addition product is favored. The X-ray structure of [(η5-C5H4SiMe3)2Ti(CtCSiMe3){µ-CdC(SiMe3)(R)}Cu], 22, which is a rare example of a 1,1-bimetallaalkene, has been solved. Crystals of 22 are pseudomerohedrally twinned and monoclinic, space group P21/c, with a ) 31.05(2) Å, b ) 14.323(3) Å, c ) 20.014(8) Å, β ) 108.53(5)°, V ) 8440(7) Å3, Z ) 8, and final R ) 0.1233 for 8564 reflections with F > 4σ(F) and 462 parameters.

Introduction Organocopper(I) and -silver(I) compounds CuR and AgR (R ) alkyl,1 alkenyl,2 alkynyl,3 aryl4), as well as inorganic copper(I) and silver(I) salts CuX and AgX (X ) alkoxide,5 phenoxide,6 * To whom correspondence should be addressed. E-mail: [email protected]. † Debye Institute, Utrecht University. ‡ Ruprecht-Karls-Universita ¨ t Heidelberg. § Universite ´ Louis Pasteur. ⊥ Bijvoet Center for Biomolecular Research, Utrecht University. | To whom correspondence pertaining to crystallographic studies should be addressed. E-mail: [email protected]. X Abstract published in AdVance ACS Abstracts, April 15, 1996. (1) Alkylcoppers. [CuCH2SiMe3]4: (a) Jarvis, J. A. J.; Pearce, R.; Lappert, M. F. J. Chem. Soc., Dalton Trans. 1977, 999. (200d >200d

8 8 ∞

3 3h 3g

13 14 15 16 17

CuMese CuC6H4CH3-4 CuC6H4OMe-4 CuC6H4NMe2-4 CuC6H5

Arylcoppers 124† 73† 98† 82† (0 (soln)

100 110-120 f 117-120 100

5 4

4d,e 4h

∞ ∞

4k 4g,h

18

AgMese

Arylsilvers 119†

f

4

4d

sp) but also by the different geometry around the metal center (CusC decreases in the order tetrahedral > trigonal planar > linear copper geometry). As an illustration one sees that the CusC14 bond length in 5 of 1.966(2) Å is somewhat longer than the corresponding distance of 1.947(2) Å in 13. This is a reflection of the lower s-orbital participation in the copper to carbon (sp3hybridized) bond in 5 as compared to that in 13 where copper is bonded to an sp2-hybridized carbon atom. The CusC bond length found in alkynylcopper complex [1‚CuCtCSiMe3] (10; 1.898(3) Å) also supports this conclusion.13b The copper-to-η2-alkyne distances in the methylcopper complex 5 (Cu1-C1 2.076(2) Å; Cu1-C2 2.080(2) Å) and in the mesitylcopper complex 13 (Cu1-C1 2.064(2) Å; Cu1-C2 2.082(2) Å) are approximately 0.21 Å shorter than the corre(23) (a) Normant, J. F.; Cahiez, G.; Chuit, C.; Villieras, J. J. Organomet. Chem. 1974, 77, 269 and 281. (b) Marfat, A.; McGuirk, P. R.; Helquist, P. J. Org. Chem. 1979, 44, 3888. (c) Carruthers, W. In ComprehensiVe Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, 1982; Vol. 7, Chapter 49, pp 661-729. (24) Alkenylcopper‚CuBr: (a) Noltes, J. G.; ten Hoedt, R. W. M.; van Koten, G.; Spek, A. L. Schoone, J. C. J. Organomet. Chem. 1982, 225, 365. (b) Smeets, W. J. J.; Spek, A. L. Acta Crystallogr. 1987, C43, 870.

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Figure 7. Interaction of bis(alkyne) chelates with electrophilic metal fragments: (left) bridging interaction, (right) η2-bonding in anionic species.

sponding distances in the mesitylsilver complex 18 (Ag1-C1 2.270(9) Å; Ag1-C2 2.305(9) Å) and reflect the smaller ionic radius of Cu+ (0.96 Å) as compared to that of Ag+ (1.26 Å).25 Similarly, the Cu-Cipso distance in 13 is 0.15 Å shorter (1.947(2) Å) than the corresponding Ag-Cipso distance in 18 (2.099(5) Å). Important observations with respect to the alkyne-copper interaction are (a) a CtC bond lengthening from 1.203(9) and 1.214(6) Å (the uncoordinated CtC bond lengths in 1)15 to 1.247(3) Å in 5, 1.250(2) Å in 13, and 1.24(1) Å in 18 and (b) bending of the TisCsC and CsCsSi units from the linear arrangement in the free ligand 1 (TisCsC and CsCsSi 177 and 176.5°, respectively) to 166.6(6) and 162.9(7)° in 18, 163.7(1) and 158.5(2)° in 5, and 163.7(1) and 155.5(2)° in 13. Bonding Description. Compounds 5-18 are the first examples of neutral monomeric organocopper (silver) units complexed by an organometallic bidentate bis(alkyne) ligand. In this sense, the well-designed 3-titanio-1,4-pentadiyne 1 is capable of diminishing the aggregation number of organocopper and organosilver structures to monomeric bis(η2-alkyne)M(η1R) entities (M ) Cu, Ag), while other ligating molecules either do not interact with organocopper and organosilver aggregates or only result in adducts with a lower polynuclearity.9,10 The experimental observation that reaction of 18 with mesitylcopper produces 13 and reaction of 21 with CuOTf produces 3, whereas the reverse reactions do not occur, leads us to conclude that the η2-alkyne-copper bonding is stronger than the η2-alkyne-silver bonding.13,15 Related reactions of organometallic bis(alkyne) chelates such as (η5-C5H5)2Ti(CtCtBu)2 and L2Pt(CtCR)2 (L2 ) 2 PPh3, dppe, COD; R ) tBu, Ph) with cis-Pt(C6F5)2(THF)2 do not stop at the stage of bis(η2-alkyne) bonding as typified for [1‚MR] (M ) Cu, Ag; 5-21). For example, the metal-containing unit Pt(C6F5)2 interacts instead with the TisCtC or PtsCtC σ-bond, which leads to a structure with an asymmetrically bridging CtC fragment. In this case the electrophilic platinum atom interacts preferentially with the CR atoms of the 3-titaniopenta-1,4-diyne (Figure 7).26a,b However, when (NBu4)2[cis-Pt(C6F5)2(CtCSiMe3)2] is reacted with [M(η3-C3H5)Cl]n (M ) Pt, n ) 4; M ) Pd, n ) 2), complexes of the type [(C6F5)2Pt(CtCSiMe3)2M(η3-C3H5)](nBu4N) are formed in which both alkynes are η2-bonded to the allylmetal moiety (Figure 7). This η2-bonding is likely to result from the lower electrophilic character since the whole species is anionic.26c In complexes [1‚MR] (M ) Cu, Ag; 5-21), the alkyne-toMR interaction can be described as arising from two compo(25) Handbook of Chemistry and Physics, 72nd ed.; Lide, D. R., Ed.; Chemical Rubber Publishing Co.: Boston, 1992. (26) (a) Berenguer, J. R.; Falvello, L. R.; Fornie´s, J.; Lalinde, E.; Toma´s, M. Organometallics 1993, 12, 6-7. (b) Fornie´s, J.; Go´mez-Saso, M. A.; Lalinde, E.; Martı´nez, F.; Moreno, M. T. Organometallics 1992, 11, 28732883. (c) Berenguer, J. R.; Fornie´s, J.; Lalinde, E.; Martı´nez, F. J. Organomet. Chem. 1994, 470, C15-C18.

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Janssen et al. ligand R in [1‚MR] (M ) Cu, Ag) from an electron-withdrawing to an electron-donating ligand or Vice Versa has a much larger influence on the 13C chemical shift of CR (TisCtC) than on that of Cβ (TisCtC). The latter observation can be explained from Figure 8, since the Cu orbitals involved in back-donation have a better overlap with the orbitals from CR than with those of Cβ. Conclusions

Figure 8. Molecular orbitals for the copper-to-alkyne back-donating interactions: (a) major in-plane contributing MO, (b) minor out-ofplane contributing MO. Note that the calculations were carried out for Cp2Ti(CtCH)2Cu(CH3) as a model system.

nents: a σ-donation of electron density from a filled π-orbital on the alkyne to a suitable empty orbital on Cu (Ag) and a back-donating component, involving the donation of electron density from a filled d-orbital on the metal to an empty π*orbital on the alkyne. A similar bonding description was already postulated on the basis of infrared spectra of alkynylcopper aggregates, but little evidence could be presented to substantiate this idea in more detail.3k EHT analysis of the molecular orbitals of the Cp2Ti(CtCH)2Cu(CH3) model system indicates that the back-bonding component in the alkyne-to-MR interaction is more important. Thus, the MR (M ) Cu, Ag) unit can be described as a nucleophile in which M represents a metal with a low Lewis acidity (electrophilicity). In fact, two combinations of π* alkyne orbitals were found to possess both suitable symmetry and energy to provide efficient interactions with a filled CuI (AgI) orbital (ds mixture). The first interaction (Figure 8a) takes place in the plane of the Ti(CtCH)2Cu entity while the second interaction (Figure 8b) occurs perpendicular to this plane. Note that in Figure 8a the overlap between the metal sd hybrid and the π* alkyne orbitals is quite important, especially with the CR atoms. In Figure 8b the overlap is of lesser extent, but again better with CR than with Cβ. The in-plane interaction shown in Figure 8a accounts for the dependence of the back-donation on the σ-donating capacity of the ligand R: more electrondonating R groups will destabilize more the sd Cu (Ag) hybrid which in turn will interact more with the π* alkyne orbitals, thus transferring more electron density into these π* alkyne orbitals. The influence of the σ-donating capacity of the ligand R in compounds [1‚MR] (M ) Cu, Ag) on the extent of backdonation is most obvious from the spectroscopic data for these compounds: more electron-donating ligands R result in a lower CtC stretching frequency, a higher CR (TisCtC), and a lower Cβ (TisCtC) 13C chemical shift, as well as in a higher distortion of the TisCtCsSi entities from linearity. Moreover, ν(CtC) seems to correlate with the deviation of the TisCsC and CsCsSi angles and with the 13C chemical shifts of both carbon atoms of the alkyne ligands. In addition, changing the

The striking property of [(η5-C5H4SiMe3)2Ti(CtCSiMe3)2] (1) to bind mononuclear metal fragments CuR or AgR gives access to a novel type of mononuclear bis(η2-alkyne)organocopper and -silver species with an η1-bonded organic ligand R. In this way organocopper compounds, i.e., CuMe, CuEt, CunBu, and CuCHdCH2, which otherwise are unstable and decompose already at low temperatures, have been stabilized and isolated as their [1‚CuR] complexes. The alkylcopper compounds [1‚CuR], 5-8, slowly decompose in solution, either Via a nucleophilic substitution reaction pathway or Via β-hydride elimination, depending on the temperature applied. At low temperature the bimetallic acetylide [(η5-C5H4SiMe3)2Ti(CtCSiMe3)(CtCCu)]213b is formed as the main product as a result of nucleophilic substitution, whereas at high temperatures the β-hydride elimination affording a CusH intermediate is more favored. These results have been discussed in terms of the alkynemetal interaction, which is dominated by the (in-plane) backdonation of electron density from the group 11 metal atom to the π*-orbital on the alkyne ligands. To our knowledge no other series in group 11 metal chemistry provides such a clear-cut demonstration of the influence of M-to-π*-alkyne back-donation. Experimental Section All experiments were carried out using standard Schlenk techniques under an inert oxygen-free nitrogen atmosphere. THF, Et2O, and C6H6 were distilled from sodium-benzophenone ketyl prior to use. CH2Cl2 was distilled from CaH2. 1H and 13C NMR spectra were recorded on a Bruker AC-200 or Bruker AC-300 spectrometer. Melting (decomposition) points were determined by using a Bu¨chi melting point apparatus or where indicated by using a Mettler TA-4000 differential scanning calorimeter. FT-IR spectra were recorded on a Mattson Galaxy 5000 series spectrometer. Elemental analyses were carried out by Dornis und Kolbe, Mikroanalytisches Laboratorium, Mu¨lheim a.d. Ruhr, and at the Organisch-Chemisches Institut der Universita¨t Heidelberg, Germany. [CuMe]∞1b (CAUTION: Dry methylcopper [CuMe]∞ is explosiVe. It can be handled as a suspension, but extreme care has to be taken with all safety precautions warranted. Work on a small scale (below 100 mg) is preferable.), [CuCH2SiMe3]4,1a [CuC6H2Me32,4,6]5, [AgC6H2Me3-2,4,6]4,4d [CuC6H4Me-4]4,4h [CuC6H4NMe2-4]∞,4k [CuC6H5]∞,4g [Cu4{C6H3(CH2NMe2)2-2,6}2Br2],19 [Li{C6H3(CH2NMe2)22,6}]2,20 and [(η5-C5H4SiMe3)2Ti(CtCSiMe3)2] (1)14a were prepared according to literature procedures. [CuC6H4OMe-4]n was prepared similar to 2-anisylcopper.4f,h Compounds [1‚CuX] (X ) Cl (2), OTf (3), SC6H4CH2NMe2-2 (4a), SC6H5 (4c), CtCSiMe3 (10), CtCtBu (11), CtCPh (12)) were synthesized as described elsewhere.13,15 Alkylcopper Compounds. Synthesis of [1‚CuMe] (5) from 1 and CuMe. To a freshly prepared suspension of CuMe (4.44 mmol based on Cu) in Et2O (30 mL) was added a solution of 1 (0.66 g, 1.28 mmol) in Et2O (10 mL). Upon addition of 1 the reaction mixture turned deep red. After stirring for 1 h the red solution was separated from the remaining solid by centrifugation and subsequent decantation of most of the supernatant (CAUTION: The solid contains CuMe and can explode when dry. Immediately after the separation an aqueous NH4Cl solution was added to the residue.). Finally, the red-colored solution was concentrated to a volume of approximately 5 mL, after which a small fraction of this solution was evaporated to dryness, leaving a red solid (for analytical and spectroscopic data Vide infra).

Monomeric Bis(η2-alkyne) Complexes of Cu(I) and Ag(I) Synthesis of [1‚CuMe] (5) from 4a and ZnMe2. To 4a (0.30 g, 0.40 mmol) in Et2O (20 mL) at 0 °C was added ZnMe2 (2 mL of a 0.21 M solution in toluene, 0.42 mmol). Upon addition the initially orange solution immediately turned deep red. After stirring for 1 h at 0 °C, all volatiles were removed in Vacuo. The product could be isolated by extraction with pentane (2 × 10 mL) and subsequent filtration of Zn(Me)SC6H4CH2NMe2-27e (yield 0.21 g (88%) of red powder). Crystals suitable for an X-ray structure determination were grown by cooling a saturated solution of 5 in Et2O to -20 °C: mp ) 143 °C dec; IR (CtC) 1867 cm-1; 1H NMR (300.13 MHz, C6D6) δ (ppm) 0.25 (s, 18 H, SiMe3), 0.46 (s, 18 H, SiMe3), 0.74 (s, 3 H, Me), 5.18 (t, 4 H, Cp, J ) 2 Hz), 5.69 (t, 4 H, Cp, J ) 2 Hz); 13C NMR (75.47 MHz, C6D6) δ (ppm) -7.4 (Me), 0.6 (SiMe3), 1.2 (SiMe3), 110.1 (Cp), 113.6 (Cp), 116.1 (ipso-Cp), 123.4 (CtCsSi), 203.6 (TisCtC). Anal. Calcd for C27H47CuSi4Ti: C, 54.46; H, 7.96; Cu, 10.67. Found: C, 54.55; H, 8.07; Cu 10.48. Synthesis of [1‚CuCH2SiMe3] (6) from 1 and CuCH2SiMe3. To CuCH2SiMe3 (0.11 g, 0.73 mmol) in Et2O (20 mL) at 25 °C was added 1 (0.38 g, 0.74 mmol) in Et2O (20 mL). After stirring the dark red reaction mixture for 3 h all volatiles were removed in Vacuo, giving 0.44 g (90%, 0.66 mmol) of red-brown 6: mp > 115 °C; IR (CtC) 1930 cm-1; FD-MS m/z (M•+) ) 668; 1H NMR (200.13 MHz, C6D6) δ (ppm) 0.26 (s, 18 H, SiMe3), 0.39 (s, 9 H, SiMe3), 0.43 (s, 18 H, SiMe3), 0.98 (s, 2 H, CH2), 5.46 (t, 4 H, Cp, J ) 2 Hz), 5.71 (t, 4 H, Cp, J ) 2 Hz); 13C NMR (50.32 MHz, C6D6) δ (ppm) 0.5 (SiMe3), 1.7 (SiMe3), 9.4 (CuCH2SiMe3), 110.8 (Cp), 114.6 (Cp), 115.6 (ipso-Cp), 125.3 (CtCsSi), 202.9 (TisCtC). CuCH2SiMe3 is not observed. Synthesis of [1‚CuCH2SiMe3] (6) from 3 and LiCH2SiMe3. To 3 (0.50 g, 0.69 mmol) in THF (100 mL) at -70 °C was added dropwise an equimolar amount of LiCH2SiMe3 (0.07 g, 0.74 mmol) in THF (50 mL). Subsequently the reaction mixture was gradually allowed to warm to 25 °C over 2 h. After stirring for another 3 h, all volatiles were removed in Vacuo. The residue was extracted with Et2O (3 × 50 mL) and filtered through Celite. Evaporation of the volatiles in Vacuo yields 0.41 g (89%) of 6 (for analytical and spectroscopic data Vide supra). Synthesis of [1‚CuEt] (7) from 4a and ZnEt2. The preparation of 7 is similar to that of 5 starting from 4a (0.15 g, 0.20 mmol) in toluene (30 mL) and ZnEt2 (0.20 mL of a 1 M solution in toluene, 0.20 mmol) (yield 0.12 g (71%) of red 7): IR (CtC) 1857 cm-1; 1H NMR (200.13 MHz, C6D6) δ (ppm) 0.26 (s, 18 H, SiMe3), 0.45 (s, 18 H, SiMe3), 1.76 (t, 3 H, CH3, J ) 7.5 Hz), 2.13 (q, 2 H, CH2, J ) 7.8 Hz), 5.17 (t, 4 H, Cp, J ) 2 Hz), 5.68 (t, 4 H, Cp, J ) 2 Hz). Since this product decomposes at temperatures above 0 °C, matching elemental analyses could not be obtained. Synthesis of [1‚CunBu] (8) from 4c and LinBu. The preparation of 8 is similar to that of 5 but starting from [1‚CuSC6H5] (4c) (0.22 g, 0.32 mmol) in pentane (30 mL) and LinBu (0.20 mL of a 1.6 M solution in hexane, 0.32 mmol) (yield 0.16 g (79%) of red 8): IR (CtC) 1851 cm-1; 1H NMR (200.13 MHz, C6D6) δ (ppm) 0.27 (s, 18 H, SiMe3), 0.47 (s, 18 H, SiMe3), 1.17 (t, 3 H, CH3, J ) 7.2 Hz), 1.6-1.8 (m, 2 H, CH2), 1.9-2.2 (m, 4 H, CH2CH2), 5.19 (t, 4 H, Cp, J ) 2 Hz), 5.69 (t, 4 H, Cp, J ) 2 Hz). Since this product decomposes at temperatures above 0 °C, matching elemental analyses could not be obtained. Alkenylcopper Compounds. Synthesis of [1‚CuC(H)dCH2] (9) from 4a and BrMgC(H)dCH2. To 4a (0.30 g, 0.40 mmol) in Et2O (15 mL) at 0 °C was added BrMgC(H)dCH2 (1.22 mL of a freshly prepared 0.33 M solution in THF, 0.40 mmol). Upon addition, the initially orange solution immediately turned deep red. After stirring for 1 h at 0 °C, all volatiles were removed in Vacuo. The product could be isolated by extraction with pentane (1 × 25 mL) and subsequent filtration of Mg(Br)SC6H4CH2NMe2-2 (yield 0.19 g (78%) of red 9): IR (CtC) 1868 cm-1, (CdC) 1585 cm-1; 1H NMR (200.13 MHz, C6D6) δ (ppm) 0.24 (s, 18 H, SiMe3), 0.48 (s, 18 H, SiMe3), 5.19 (t, 4 H, Cp, J ) 2 Hz), 5.67 (t, 4 H, Cp, J ) 2 Hz), 5.96 (dd, 1 H, dCH2, Jtrans ) 19.6 Hz, Jgem ) 3.4 Hz), 6.82 (dd, 1 H, dCH2, Jcis ) 12.5 Hz, Jgem ) 3.4 Hz), 7.77 (dd, 1 H, CuC(H)d, Jtrans ) 19.6 Hz, Jcis ) 12.5 Hz); 13C NMR (50.32 MHz, C6D6) δ (ppm) 0.6 (SiMe3), 1.3 (SiMe3), 110.4, 113.6 (Cp), 112.1, 115.2, 116.7 (ipso-Cp and vinyl), 125.3 (CtCsSi), 199.3 (TisCtC). Since this product decomposes at temperatures above 0 °C, matching elemental analyses could not be obtained. Arylcopper Compounds. Synthesis of [1‚CuC6H2Me3-2,4,6] (13) from 1 and CuC6H2Me3-2,4,6. To CuC6H2Me3-2,4,6 (0.19 g, 1.04

J. Am. Chem. Soc., Vol. 118, No. 20, 1996 4827 mmol) in THF (15 mL) was slowly added 1 (0.54 g, 1.04 mmol) in THF (25 mL). On addition of 1 the yellow solution immediately turned dark red. After stirring for 0.5 h the solvent was removed in Vacuo. X-ray suitable crystals could be obtained by crystallization from a concentrated solution in Et2O at -20 °C (yield 0.61 g (84%) of crystalline 13): mp (DSC) ) 113.9 °C; IR (CtC) 1856 cm-1; FD-MS m/z (M•+) ) 698; 1H NMR (300.13 MHz, C6D6) δ (ppm) 0.11 (s, 18 H, SiMe3), 0.30 (s, 18 H, SiMe3), 2.36 (s, 3 H, p-Me), 2.37 (s, 6 H, o-Me), 5.17 (t, 4 H, Cp, J ) 2 Hz), 5.82 (t, 4 H, Cp, J ) 2 Hz), 6.99 (s, 2 H, ArH); 13C NMR (75.47 MHz, C6D6) δ (ppm) 0.2 (SiMe3), 0.6 (SiMe3), 21.4 (p-Me), 28.0 (o-Me), 110.7 (Cp), 113.0 (Cp), 116.7 (ipsoCp), 125.0 (CtCsSi), 126.3 (Ar-3), 133.6 (Ar-4), 145.2 (Ar-2), 201.8 (TisCtC); mesityl Cipso is not observed. Anal. Calcd for C35H55CuSi4Ti: C, 60.09; H, 7.92; Cu 9.08. Found: C, 59.96; H, 7.90; Cu, 8.94. Synthesis of [1‚CuC6H2Me3-2,4,6] (13) from 2 and LiC6H2Me32,4,6. To 2 (0.50 g, 0.81 mmol) in THF (100 mL) at -70 °C was added dropwise an equimolar amount of LiC6H2Me3-2,4,6 (0.10 g, 0.79 mmol) in THF (50 mL). Subsequently the reaction mixture was gradually allowed to warm to 25 °C over 2 h and stirred for another 3 h. After removal of all volatiles in Vacuo, the residue was extracted with Et2O (3 × 50 mL) and filtered through Celite. Evaporation of the volatiles in Vacuo yielded 0.43 g (78%) of 13 (for analytical and spectroscopic data Vide supra). Synthesis of [1‚CuC6H2Me3-2,4,6] (13) from 3 and LiC6H2Me32,4,6. This preparation is similar to the one described from 2, but starting from 3 (0.50 g, 0.69 mmol) and an equimolar amount of LiC6H2Me3-2,4,6 (0.09 g, 0.71 mmol) (yield 0.40 g (83%) of 13) (for analytical and spectroscopic data Vide supra). Synthesis of [1‚CuC6H4Me-4] (14) from 1 and CuC6H4Me-4. To a suspension of CuC6H4Me-4 (0.27 g, 1.73 mmol) in THF (15 mL) was slowly added 1 (0.90 g, 1.74 mmol) in THF (15 mL). On addition of 1, the slightly green suspension turned dark red, and finally resulted in a clear red solution. After stirring for 4 h, the solution was filtered, and all volatiles were removed in Vacuo. Crystallization from Et2O at -20 °C afforded an orange powder, which could be identified as [1‚ CuBr]. After a second filtration and concentration of the solution, 14 could be isolated as a red powder (yield 0.69 g (59%)) (for analytical and spectroscopic data Vide infra). Synthesis of [1‚CuC6H4Me-4] (14) from 4a and LiC6H4Me-4. To freshly prepared LiC6H4Me-4 (0.04 g, 0.41 mmol) in Et2O (25 mL) at 0 °C was slowly added 4a (0.30 g, 0.40 mmol) in one portion. The reaction mixture turned deep red, and LiSC6H4CH2NMe2-227 precipitated. After stirring for 3 h at temperatures below 0 °C, all volatiles were removed in Vacuo. 14 could be isolated by extraction with pentane and subsequent filtration of LiSC6H4CH2NMe2-227 (yield 0.25 g (93%) of red 14): mp ) 73 °C dec; IR (CtC) 1862 cm-1; 1H NMR (300.13 MHz, C7D8, 253 K) δ (ppm) 0.16 (s, 18 H, SiMe3), 0.27 (s, 18 H, SiMe3), 2.30 (s, 3 H, Me), 5.15 (t, 4 H, Cp, J ) 2 Hz), 5.72 (t, 4 H, Cp, J ) 2 Hz), 7.16 (d, 2 H, ArH, J ) 6.9 Hz), 7.67 (d, 2 H, ArH, J ) 6.9 Hz); 13C NMR (75.47 MHz, C7D8, 253 K) δ (ppm) 0.5 (SiMe3), 0.8 (SiMe3), 22.9 (p-Me), 110.4 (Cp), 113.2 (Cp), 116.5 (ipso-Cp), 125.9 (CtCsSi), 127.9, (Ar-3) 131.9 (Ar-4), 141.6 (Ar-2), 158.5 (Ar-ipso), 199.3 (TisCtC); signals from Ar-2 and Ar-3 have been tentatively assigned. Since this product decomposes at temperatures above 0 °C, matching elemental analyses could not be obtained. Synthesis of [1‚CuC6H4OMe-4] (15) from 1 and CuC6H4OMe-4. This preparation is similar to that described for 14 but starting from CuC6H4OMe-4 (0.10 g, 0.59 mmol) in Et2O (20 mL) and 1 (0.30 g, 0.58 mmol) in Et2O (20 mL) (yield 0.24 g (60%)) (for analytical and spectroscopic data Vide infra). Synthesis of [1‚CuC6H4OMe-4] (15) from 4a and LiC6H4OMe4. To freshly prepared LiC6H4OMe-4‚LiBr (0.10 g, 0.50 mmol) in Et2O (30 mL) at 0 °C was added 4a (0.38 g, 0.50 mmol) in one portion. The reaction mixture turned deep red, and LiSC6H4CH2NMe2-227 precipitated. After stirring for 2 h at temperatures below 0 °C, all volatiles were removed in Vacuo. 15 could be isolated by extraction with pentane and subsequent filtration of LiSC6H4CH2NMe2-227 and LiBr (yield 0.26 g (75%) of red 15): mp ) 98 °C dec; IR (CtC) (27) Janssen, M. D.; Rijnberg, E.; de Wolf, C. A.; Hogerheide, M. P.; Kruis, D.; Kooijman, H.; Spek, A. L.; Grove, D. M.; van Koten, G. Inorg. Chem., submitted for publication.

4828 J. Am. Chem. Soc., Vol. 118, No. 20, 1996 1865 cm-1; 1H NMR (300.13 MHz, C7D8, 253 K) δ (ppm) 0.19 (s, 18 H, SiMe3), 0.29 (s, 18 H, SiMe3), 3.47 (s, 3 H, OMe), 5.16 (t, 4 H, Cp, J ) 2 Hz), 5.74 (t, 4 H, Cp, J ) 2 Hz), 7.02 (d, 2 H, ArH, J ) 7.6 Hz), 7.64 (d, 2 H, ArH, J ) 7.6 Hz); 13C NMR (75.47 MHz, C7D8, 253 K) δ (ppm) 0.3 (SiMe3), 0.5 (SiMe3), 54.0 (OMe), 110.5 (Cp), 113.3 (Cp), 116.6 (ipso-Cp), 126.0 (CtCsSi), 132.3 (Ar-4), 141.8 (Ar-2), 157.5 (Ar-ipso), 199.1 (TisCtC); the signal from Ar-3 could not be observed; signals from Ar-2 and Ar-3 have been tentatively assigned. Since this product decomposes at temperatures above 0 °C, matching elemental analyses could not be obtained. Synthesis of [1‚CuC6H4NMe2-4] (16) from 1 and CuC6H4NMe24. This preparation is similar to that described for 14, but starting from CuC6H4NMe2-4 (0.15 g, 0.82 mmol) in Et2O (50 mL) and 1 (0.50 g, 0.81 mmol) (yield 0.50 g (88%)) (for analytical and spectroscopic data Vide infra). Synthesis of [1‚CuC6H4NMe2-4] (16) from 4a and LiC6H4NMe24. To freshly prepared LiC6H4NMe2-4‚LiBr (0.04 g, 0.19 mmol) in Et2O (25 mL) at 0 °C was added 4a (0.14 g, 0.19 mmol) in one portion. The reaction mixture turned deep red, and LiSC6H4CH2NMe2-227 precipitated. After stirring for 1 h at -20 °C, all volatiles were removed in Vacuo. 16 could be isolated by extraction with pentane and subsequent filtration of LiSC6H4CH2NMe2-227 and LiBr (yield 0.12 g (91%) of red 16): mp ) 82 °C dec; IR (CtC) 1863 cm-1; 1H NMR (300.13 MHz, C7D8, 253 K) δ (ppm) 0.23 (s, 18 H, SiMe3), 0.30 (s, 18 H, SiMe3), 2.66 (s, 6 H, NMe2), 5.16 (t, 4 H, Cp, J ) 2 Hz), 5.74 (t, 4 H, Cp, J ) 2 Hz), 6.89 (s, 2 H, ArH, J ) 8.0 Hz), 7.65 (s, 2 H, ArH, J ) 8.0 Hz). 13C NMR (75.47 MHz, C7D8, 253 K) δ (ppm) 0.5 (SiMe3), 0.7 (SiMe3), 40.8 (NMe2), 110.3 (Cp), 113.2 (Cp), 116.3 (ipso-Cp), 125.7 (CtCsSi), 141.8 (Ar-2), 148.2 (Ar-ipso), 200.1 (TisCtC); the signals from Ar-3 and Ar-4 are not observed; signals from Ar-2 and Ar-3 have been tentatively assigned. Since this product decomposes at temperatures above 0 °C, matching elemental analyses could not be obtained. Synthesis of [1‚CuC6H5] (17) from 1 and CuC6H5. This preparation is similar to that described for 14, but starting from a suspension of CuC6H5 (0.34 g, 2.42 mmol) in THF (20 mL) and 1 (1.25 g, 2.42 mmol) in THF (20 mL) (yield 0.56 g (35%)) (for analytical and spectroscopic data Vide infra). Synthesis of [1‚CuC6H5] (17) from 4a and LiC6H5. To freshly prepared LiC6H5 (0.04 g, 0.48 mmol) in Et2O (25 mL) at 0 °C was added 4a (0.35 g, 0.47 mmol) in one portion. The reaction mixture turned deep red, and LiSC6H4CH2NMe2-227 precipitated. After stirring for 1.5 h at -20 °C, all volatiles were removed in Vacuo. The product could be isolated by extraction with pentane and subsequent filtration of LiSC6H4CH2NMe2-227 (yield 0.30 g (97%) of red 17): IR (CtC) 1861 cm-1; 1H NMR (300.13 MHz, C7D8, 253 K) δ (ppm) 0.16 (s, 18 H, SiMe3), 0.27 (s, 18 H, SiMe3), 5.15 (t, 4 H, Cp, J ) 2 Hz), 5.72 (t, 4 H, Cp, J ) 2 Hz), 7.16 (t, 1 H, ArH, J ) 7.0 Hz), 7.31 (t, 2 H, ArH, J ) 7.2 Hz), 7.77 (d, 2 H, ArH, J ) 7.2 Hz); 13C NMR (75.47 MHz, C7D8, 253 K) δ (ppm) 0.5 (SiMe3), 0.7 (SiMe3), 110.5 (Cp), 113.3 (Cp), 116.6 (ipso-Cp), 123.6 (Ar-4), 126.0 (CtCsSi), 127.0 (Ar-3), 141.8 (Ar-2), 163.9 (Ar-ipso), 199.0 (TisCtC). Since this product decomposes at temperatures above 0 °C, matching elemental analyses could not be obtained. Arylsilver Compounds. Synthesis of [1‚AgC6H2Me3-2,4,6] (18) from 1 and AgC6H2Me3-2,4,6. To AgC6H2Me3-2,4,6 (0.58 g, 2.55 mmol) in Et2O (15 mL) was slowly added a solution of 1 (1.22 g, 2.36 mmol) in Et2O (25 mL). On addition of 1, the slightly yellow solution immediately turned deep purple. After stirring for 1 h, the clear violet solution was concentrated in Vacuo. Crystalline 18 could be obtained by crystallization from a concentrated solution in Et2O at -20 °C: mp ) 119 °C dec; IR (CtC) 1902 cm-1; FD-MS m/z (M•+) ) 744; 1H NMR (300.13 MHz, C6D6) δ (ppm) 0.21 (s, 18 H, SiMe3), 0.26 (s, 18 H, SiMe3), 2.39 (s, 3 H, p-Me), 2.57 (s, 6 H, o-Me), 5.40 (t, 4 H, Cp, J ) 2 Hz), 5.89 (t, 4 H, Cp, J ) 2 Hz), 7.10 (s, 2 H, ArH); 13C NMR (75.47 MHz, C6D6) δ (ppm) 0.4 (SiMe3), 0.6 (SiMe3), 21.5 (p-Me), 29.7 (o-Me), 112.9 (Cp), 115.1 (Cp), 119.6 (ipso-Cp), 125.6 (d, Ar3,5, 3J(Ag, C) ) 7 Hz), 125.8 (d, CtCsSi, J(Ag, C) ) 7 Hz), 133.4 (Ar-4), 144.6 (Ar-2,6), 168.3 (dd, Ar-1, 1J(107Ag, 13C) ) 142, 1J(109Ag, 13C) ) 164 Hz), 184.5 (d, TisCtC, J(Ag, C) ) 3 Hz). Anal. Calcd for C35H55AgSi4Ti: C, 56.51; H, 7.45. Found: C, 56.28; H, 7.54.

Janssen et al. Addition Product 22. Synthesis of [(η5-C5H4SiMe3)2Ti(CtCSiMe3){µ-CdC(SiMe3)(C6H3(CH2NMe2)2-2,6)Cu}] (22). To [Cu4(C6H3(CH2NMe2)2-2,6)2Br2] (0.38 g, 0.48 mmol of Cu4 aggregate) in Et2O (50 mL) was added in one portion 1 (0.99 g, 1.92 mmol) at 25 °C. The reaction mixture gradually turned deep red, and after stirring for 3 h all volatiles were evaporated in Vacuo. Extraction with pentane (3 × 40 mL) and subsequent evaporation of the volatiles in Vacuo yielded 0.64 g (86%, 0.83 mmol) of 22. The residue is [1‚CuBr] (0.63 g, 0.95 mmol, 100%), as was established by comparison of the analytical and spectroscopic data to an authentic sample.28 Crystalline 22 can be obtained by cooling a saturated Et2O solution to -20 °C: mp ) 138 °C dec; IR (CtC) 1882 cm-1, (CdC) 1591 cm-1; 1H NMR (300.13 MHz, C6D6) δ (ppm) 0.21 (s, 18 H, SiMe3), 0.28 (s, 18 H, SiMe3), 2.35 (br s, 12 H, NMe2), 4.05 (br s, 4 H, CH2), 4.9 (br s, 4 H, Cp), 5.1 (br s, 4 H, Cp), 7.08 (m, 3 H, ArH); 1H NMR (300.13 MHz, C6D6, 237 K) δ (ppm) 0.15 (s, 9 H, SiMe3), 0.27 (s, 9 H, SiMe3), 0.34 (s, 9 H, SiMe3), 0.48 (s, 9 H, SiMe3), 2.10 (s, 3 H, NMe2), 2.20 (s, 3 H, NMe2), 2.44 (s, 6 H, NMe2), 2.50 (d, 1 H, 2J ) 10 Hz, CH2), 3.91 (s, 2 H, CH2), 4.11 (d, 1 H, 2J ) 10 Hz, CH2), 5.21 (s, 2 H, Cp), 5.27 (s, 1 H, Cp), 5.34 (s, 1 H, Cp), 5.45 (s, 1 H, Cp), 5.82 (s, 1 H, Cp), 6.05 (s, 1 H, Cp), 6.17 (s, 1 H, Cp), 6.79 (d, 1 H, 3J ) 7 Hz, ArH), 7.13 (m, 1 H, ArH), 8.02 (d, 1 H, 3J ) 8 Hz, ArH). Synthesis of 22 from [Li{C6H3(CH2NMe2)2-2,6}]2 and 4a. To [Li{C6H3(CH2NMe2)2-2,6}]2 (0.17 g, 0.23 mmol) in Et2O (20 mL) at 0 °C was added 4a (0.05 g, 0.25 mmol) in Et2O (20 mL). Cooling was stopped, and after stirring for 1 h at 25 °C all volatiles were removed in Vacuo. Extraction with pentane (30 mL) and subsequent filtration of LiSC6H4CH2NMe2-227 gave 0.17 g (97%) of 22 (for spectroscopic data Vide supra). Structure Determination and Refinement of 5, 13, 18, and 22. Crystal data and numerical details of the structure determinations are given in Table 7. Crystals of the four complexes were glued on top of glass fibers and transferred to an Enraf-Nonius CAD4T rotating anode diffractometer for data collection at 150 K. Accurate unit cell parameters and orientation matrices were derived from the setting angles of 25 well-centered reflections (SET4)29 in the range 11° < θ < 14°, and the unit cell parameters were checked for the presence of higher lattice symmetry.30 All data were collected in the ω/2θ scan mode, data were corrected for Lorentz polarization effects and for the observed linear decay of the intensity control reflections, and redundant data were merged into a unique data set. An empirical absorption correction was applied for 5, 13, and 18 using the DIFABS31 method as implemented in PLATON.32 The structures of 5, 13, and 18 were solved by automated Patterson methods using DIRDIF9233 for 5 and 18 and SHELXS8634 for 13 followed by subsequent difference Fourier techniques. The structure of complex 22 was solved by direct methods (SHELXS86)34 and difference Fourier techniques. The crystal of 22 is pseudomerohedrally twinned by a 2-fold axis coinciding with a*. The twinning (with twin index 1) was taken into account using the “TWIN” option of the SHELXL9335 program, resulting in a twin ratio of 0.325(3):0.675(3). Hydrogen atoms in 5 with the exception of those on C(14) were located from difference Fourier maps and refined with individual isotropic atomic displacement parameters. Hydrogen atoms of 13, 18, of 22 and on the C(14) methyl in 5 were introduced at calculated positions and refined riding on their carrier atoms. All nonhydrogen atoms of 5, 13, and 18 were refined with anisotropic atomic displacement parameters. In view of the twinning and the related limited quality of the data of complex 22, only the Cu, Ti, and Si atoms were refined with anisotropic atomic displacement parameters; all other (28) Lang, H.; Ko¨hler, K.; Herres, M.; Rheinwald, G.; Zsolnai, L. To be published. (29) de Boer, J. L.; Duisenberg, A. J. M. Acta Crystallogr. 1984, A40, C410. (30) Spek, A. L. J. Appl. Crystallogr. 1988, 21, 578. (31) Walker, N.; Stuart, D. Acta Crystallogr. 1983, A39, 158-166. (32) Spek, A. L. Acta Crystallogr. 1990, A46, C34. (33) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; Garcı´a-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykalla, C. The DIRDIF Program System, Technical report of the Crystallography Laboratory, University of Nijmegen, The Netherlands, 1992. (34) Sheldrick, G. M. SHELXS86. Program for crystal structure determination, University of Go¨ttingen, Go¨ttingen, Federal Republic of Germany, 1986. (35) Sheldrick, G. M. SHELXL93. Program for crystal structure refinement, University of Go¨ttingen, Go¨ttingen, Germany, 1993.

Monomeric Bis(η2-alkyne) Complexes of Cu(I) and Ag(I)

J. Am. Chem. Soc., Vol. 118, No. 20, 1996 4829

Table 7. Experimental Data for the X-ray Diffraction Studies of 5, 13, 18, and 22 5 formula formula weight space group crystal system Z a (Å) b (Å) c (Å) β (deg) volume (Å3) dcalc (g cm-3) temperature (K) F(000) µ(Mo KR) (cm-1) crystal size (mm) radiation (Å) θmin, θmax (deg) scan (ω/2θ mode) horiz aperture (mm) vert aperture (mm) decay, X-ray time h;k;l (min, max) DIFABSa no. of total, unique reflns (Rav) no. of observed reflns Nref, Npar weight (w-1)c Rd wR/wR2 S resd dens (e/Å3)

C27H47CuSi4Ti 595.44 C2/c monoclinic 4 19.477(1) 10.3622(6) 16.395(1) 95.287(5) 3294.8(3) 1.200 150 1264 10.5 0.25 × 0.55 × 0.55 Mo KR (0.710 73) 2.1, 27.5 0.62 + 0.35 tan (θ) 3.00 4.00 4σ(F))b 3784, 240 σ2(Fo2) + (0.0439P)2 + 0.51P 0.0304f 0.0766f 1.03 -0.29, 0.36

13

18

C35H55CuSi4Ti 699.59 Pbcn orthorhombic 4 12.4290(9) 19.8770(8) 15.532(1)

C35H55AgSi4Ti 743.91 Pbcn orthorhombic 4 12.47(3) 20.00(3) 15.53(3)

3837.2(4) 1.211 150 1488 9.0 0.30 × 0.50 × 0.50 Mo KR (0.710 73) 1.90, 26.48 0.50 + 0.35 tan(θ) 3.00 4.00 2.5σ(I)) 3082, 217 σ2(F) 0.026e 0.031e 1.14 -0.38, 0.27

3873(13) 1.276 150 1560 8.5 0.25 × 0.25 × 0.25 Mo KR (0.710 73) 1.02, 25.00 0.80 + 0.35 tan(θ) 3.00 4.00 4%, 15 h 0, 18; -14, 14; 0, 23 0.776, 1.262 7273, 3393 (0.047) 2068 (I > 2.5 σ(I)) 2068, 188 σ2(F) + 0.00085F2 0.055e 0.063e 3.95 -0.93, 0.88

22 C38H63N2CuSi4Ti 771.70 P21/c monoclinic 8 31.05(2) 14.323(3) 20.014(8) 108.53(5) 8440(7) 1.215 150 3296 8.3 1.00 × 0.10 × 0.05 Mo KR (0.710 73) 0.69, 25.00 0.89 + 0.35 tan(θ) 3.91 4.00 0.2%, 42 h -36, 35; 0, 17; 0, 23 15988, 14825 12882 (Fo2 > 0)b 12882, 462 σ2(Fo2) + (0.2281P)2 0.1233f 0.3432f 1.033 -1.37, 3.31

a Correction range. b All reflections used in the refinement. c P ) (max(F 2, 0) + 2F 2)/3. d R ) ∑|F | - F |/∑|F |. e Refinement on F: wR ) o c o c o {∑w(|Fo| - |Fc|)2/∑w|Fo|2}1/2. f Refinement on F2: wR2 ) {∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]}1/2.

non-hydrogen atoms in this complex were refined with individual isotropic atomic displacement parameters. Refinement of the structures with full-matrix least-squares techniques was carried out either on F (13 and 18) using reflections with I > 2.5σ(I) (SHELX76)36 or on F2 (5 and 22) using all unique reflections (5) or unique reflections with Fo2 > 0 (22) (SHELXL93).35 Complex 22 contains some solvent accessible voids of about 35 Å3; no residual (integrated) electron density was found in these areas (PLATON).32 The final difference map of 22 shows residual densities in the range -1.37 to +3.31 e/Å3 probably due to residual twinning effects. Neutral atom scattering factors for 13 and 18 were taken from Cromer and Mann37 and corrected for anomalous dispersion.38 Neutral atom scattering factors and their anomalous dispersion corrections for 5 and 22 were taken from the International Tables for Crystallography.39 Geometrical calculations and illustrations were performed with the PLATON package;32 all calculations were performed on a DEC-5000 cluster. (36) Sheldrick, G. M. SHELX76. Program for crystal structure analysis, University of Cambridge, U.K., 1976. (37) Cromer, D. T.; Mann, J. B. Acta Crystallogr. 1968, A24, 321. (38) Cromer, D. T.; Liberman, D. J. Chem. Phys. 1970, 53, 1981. (39) Wilson, A. J. C., Ed. International Tables for Crystallography; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992; Vol. C.

Acknowledgment. We gratefully thank Dr. H. Kooijman for the X-ray data collection of 22. This work was supported in part (W.J.J.S., A.L.S.) by the Netherlands Foundation for Chemical Research (SON) with financial aid from the Netherlands Organization for Scientific Research (NWO) and in part by the Deutsche Forschungsgemeinschaft, the Hermann Schlosser Stiftung Degussa AG/Frankfurt (K.K.), and the Fonds der Chemischen Industrie (Germany). Supporting Information Available: Tables of crystal data, details of the structure determination, final coordinates and equivalent isotropic thermal parameters of the non-hydrogen atoms, hydrogen atom positions and isotropic thermal parameters, anisotropic thermal parameters, and bond distances and angles for 5, 13, 18, and 22 (42 pages). This material is contained in many libraries on microfiche, immediately follows this article in the microfilm version of the journal, can be ordered from the ACS, and can be downloaded from the Internet; see any current masthead page for ordering information and Internet access instructions. JA954041K