1657
Organometallics 1995,14, 1657-1666
Lewis Base Stabilized Transition Metal Complexes of Divalent Silicon Species Bhanu P. S. Chauhan, Robert J. P. Corriu,* GBrard F. Lanneau," and Christian Priou Laboratoire des Prdcurseurs Organomdtalliques de MatLriaux, UMR 044, Universitd Montpellier 11, Case 007, Place Eugkne Bataillon, 34095 Montpellier Cedex 05, France
Norbert Auner, Hermann Handwerker, and Eberhardt Herdtweck Anorganisch-Chemisches Institut, Technische Universitat Miinchen, Lichtenbergstrasse 4, 85748 Garching, Germany Received November 10, 1994@ A direct photochemical synthesis of silanediyl-iron tetracarbonyl complexes PhzSi(B)-Fe(COk [B = 1,3-dimethylimidazolidinone(DMI) or hexamethylphosphoric triamide (HMPA)] is described. The Lewis base character of DMI is strong enough to quantitatively convert the dimeric [Fe2(CO)s(SiPh2)2]to more stable PhzSi(DMI)-Fe(CO)4. A series of organosilanediyl-transition metal complexes, of general formula ArAr'Si=MLn [Ar = Ph, Ar' = [2-(Me2NCH2)CsH41,[ ~ - ( M ~ ~ N C H ~ ) C I[ O ~H - (~MI ,~ ~ N ) C IAr, O HAr' ~ ~=; [2-(Me2NC&)CsH41; Ar = 1-Np, Ar' = [ ~ - ( M ~ ~ N C H ~ ) Cor~Ar O H=~Me, ] ; Ar' = [2-(Me2NCH2)C6H411 is directly obtained in the photochemical reaction of ArAr'SiH2 with Fe(C0)5, Cr(CO)6, Mo(CO)s, and RCpMn(CO), (R = Me, H). Single-crystal X-ray structure analysis of the complex [2-(Me2NCHz)CsH4]CsHsSi=Fe(C0)4(5a) reveals a N-Si bond length of 1.962(2)A and Si-Fe bond distance of 2.259(1) A. The sum of bond angles at silicon, excluding the N-atom, is to 346.7'. Crystal data: Cl9HI7FeNO4Si,triclinic, space group P1 (No. 2), a = 8.284(2), b = 8.404(2), c = 13.497(3) A; a = 97.02(1)",,l3 = 93.68(1)", y = 91.25(1)", V = 930.3 A3, 2 = 2, R = 0.027, Ro = 0.030 based on 3171 reflections with (I > 0.00, all data). Strong intramolecular donor stabilization with the 8-[(dimethylamino)methyllnaphthylligand directly bonded to the silicon atom prevents further reactions, but typical experiments have been performed with less coordinated 8-[(dimethylamino)methyl]phenyl derivatives. Silanediyl-iron tetracarbonyl complexes react with acetylenes, dienes, and alcohols under W irradiation, and trapping products of silylenes are isolated in good yields. A comparative study of different coordinating ligands has been carried out.
Introduction The hypothetical participation of silanediyl-transition metal complexes1in the chemical transformations of organosilicon compounds is a subject under active research.2 Although complexes of germanium(I1) and tin(I1) with group 5 and group 6 metal carbonyls are readily accessible, either from carbene-like species3 or from dihalides Y2MX2 ,4 through dehalogenation with transition metal dianionic species, the dehalogenation method has only recently been applied to the synthesis of organosilanediyl-transition metal complexe~.~ The reactions were performed in coordinating solvents, and products were isolated as monomeric stable species, ~~~
~
~~~~~
~
Abstract published in Advance ACS Abstracts, March 1, 1995. (1) For recent reviews, see: (a) Tilley, T. D. In The Silicon Heteroatom Bond; Patai', S., Rappoport, Z., Eds.; Wiley: New York, 1991;pp 245-309. (b) Zybill, C. Top. Curr. Chem. 1991,160, 1. (c) Lickiss, P. D. Chem. Soc. Rev. 1992,21,271. (d) Tilley, T. D. Acc. Chem. Res. 1993, 26, 22. (e) Zybill, C.; Handwerker, H.; Friedrich, H. Adu. Organomet. Chem. 1994,36,229. (2)(a) Aitken, C. T.; Harrod, J . F.; Samuel, E. J. Am. Chem. SOC. 1986,108, 4059. (b) Aitken, C. T.; Harrod, 3. F.; Gill, U. S. Can. J . Chem. 1987,65, 1804.(c) Hayashi, T.; Yamashita, H.; Tanaka, M.; Goto, M. Organometallics 1992,11, 3227.(d) Campbell, W. H.; Hilty, T. K.; Yurga, L. Organometallics 1989,8,2615.(e) Xin, S.;Aitken, C. T.; Harrod, J. F.; Mu, Y.; Samuel, E. Can. J . Chem. 1990,68, 471.(0 Corey, J. Y.; Zhu X.; Bedard, T. C.; Lange, L. D. Organometallics 1991, 10,924 (g) Mu, Y.; Aitken, C. T.; Cote, B.; Harrod, J. F.; Samuel, E. Can. J . Chem. 1991, 69,264. (h) Banovetz, J. P.; Stein, K. M.; Waymouth, R. M. Organometallics 1991, 10, 3430.(i) Heyn, R. H.; Tilley, T. D. J . A m . Chem. SOC.1992,114, 1917. @
containing a solvent molecule coordinated to the unsaturated silicon (eq 1). y\ y,
. /
x
+
Na2[MLn-i]
- 7= B
y\
y0
B
(1) MLn.r
Transition metal compounds with a-bonded silicon species are accessible by insertion of the Si-H bond (3)(a) Jutzi, P.;Steiner, W. Chem. Ber. 1976,109,3473.(b) Jutzi, P.; Steiner, W. Konig, E.; Huttner, G.; Frank, A.; Schubert, U. Chem. (c) Petz, W. Chem. Reu. 1986,86,1019.(d) Barrau, Ber. 1978,111,606. J.; Escudi6, J.; Satg6, J. Chem. Rev. 1990,90,283.(e) Lappert, M F.; Rowe, R. S. Coord. Chem. Rev. 1990,100, 267. (D Neumann, W. P. Chem. Rev. 1991,91,311.(g) Tokitoh, N.; Manmaru, K.; Okazaki, R. Organometallics 1994,13, 167.(h) Lappert, M. F.; Maskell, R. V. J . Organomet. Chem. 1984,264,217.(i) Veith, M.;Becker, S.; Huch, V. Angew. Chem., Int. Ed. Engl. 1990,29,216.(j) Ellis, E. L.; Hitchcock, P. B.; Holmes, S.A,; Lappert, M. F.; Slade, M. J. J. Organomet. Chem. 1993,444,95. (4)(a)Marks, T.J. J . Am. Chem. SOC.1971,93,7090.(b) Marks, 'I. J.;Newman, A. R. J. Am. Chem. SOC.1973,95,769.( c )Jastrzebski, J. T. B. H.; Van Der Schaaf, P. A.; Boersma, J.; Van Koten, G.; Heijdenrijk, D.; Goubitz, K.; De Ridder, D. J. A. J. Organomet. Chem. 1989,36,7,55. (d) Lee, K.;Arif, A. M.; Gladysz; J. A. Organometallics 1991,10,751. (e) Cotton, J. D.; Davis, P. J.; Goldberg, D. E.; Lappert, M. F.; Thomas, K. M. J . Chem. Soc., Chem. Commun. 1974,893.(D Huttner, G.; Weber, U.; Sigwarth, B.; Scheidsteger, 0.; Lang, H.; Zsolnai, L. J. Organomet. Chem. 1985,282,331. (5)(a) Zybill, C.; Muller, G.; Angew. Chem., Int. Ed. Engl. 1987,26, 669.(b) Zybill, C.; Wilkinson, D. L.; Leis, C.; Muller, G. Angew. Chem., Int. Ed. Engl. 1988,27, 583. (c) Leis, C.; Zybill, C.; Lachmann, J.; Muller, G. Polyhedron 1991,10, 1163.(d) Leis, C.; Wilkinson, D. L.; Handwerker, H.; Zybill, C.; Muller, G. Organometallics 1992,11,514.
0276-7333/95/2314-1657$09.00/00 1995 American Chemical Society
1658 Organometallics, Vol. 14, No. 4, 1995
Chauhan et al.
Scheme 2. Photolysis of Silanes 4a and 4b with Transition Metal Carbonyls
Scheme 1 Ph,SiH2
- ''
Fe(CO),
+
1
I
Ph,Si
hv
Pentane
'
Fe (GO) 'SiPh, FdO,
,
Ph hv/B
Pentane
~
Ph
- Si = Fe(C0) t
~
hvlB Toluene
B
B = DMI (3),HMPA (4)
under photochemical conditions.6 Irradiation of dihydrosilanes allowed the synthesis of dimers7 (eq 2).
-
Mn. The effect of the intramolecular coordination with aminoaryl groups upon the lability of the Si6+-H6- bond parallels the ability of these systems to form silanediyll* complexes. The dihydrosilanes with an intramolecular six-membered-ring coordinating ligand are known to be more reactive than the compounds with five-memberedring ligands (Chart 1). For example, they react with acyl chlorides,"" heterocumulenes,'lbBdketo groups,23and alcohols.20 The same ligand is more efficient at stabilizing low-coordinated silicon species, silanethiones, silaimines, and silaphos(18)Corriu, R. J. P.; Lanneau, G. F.; Chauhan, B. P. S. Organometallics 1993, 12, 2001. (19)Straus, D. A.; Grumbine, S. D.; Tilly, T. D. J . A m . Chem. SOC. 1990, 112, 7801. (20) (a) Corriu, R. J. P.; Lanneau, G. F.; Perrot, M. Tetrahedron Lett. 1987, 28, 3941. (b) Boyer, J.; BreliBre, C.; Carr6, F.; Corriu, R. J. P.; Kpoton, A.; Poirier, M.; Royo, G.; Young, J. C. J . Chem. Soc., Dalton Trans. 1989, 43. (c) Boyer, J.; Breliere, C.; Corriu, R. J . P.; Kpoton, A,; Poirier, M.; Royo, G. J . Organomet. Chem. 1986, 311, C39. (d) Corriu. R. J. P.: KDoton, A.: Poirier, M.: Rovo, G.: Corev, J. Y. J . Organomet. Chem. i986,277, C25. (21) ( a ) Ishikawa, M.; Ohi, F.; Kumada, M. J. Organomet. Chem. 1975, 186, C23. (b) Okinoshima, H.; Yamamoto, K.; Kumada, M. J. A m . Chem. Soc. 1972,94,9263. (c) Ishikawa, M. Organomet. Syn. 1988, 4, 527. (d) For a recent review on d o l e s , see: Dubac, C.; Laporterie, A.; Manuel, G. Chem. Reo. 1990, 90, 215. (22) Ittel, S. D.; Tolman, C. A.; Krusic, P. J.;English, A. D.; Jesson, J . P. Inorg. Chem. 1978, 17, 3432.
Divalent Silicon-Transition Metal Complexes phenes.13 The stability of the system is also emphasized when the reactivity of the silanediyl complexes is considered. The N6 model is strongly coordinated to the metal, preventing any approach of a nucleophile. More drastic conditions allow decomposition of the complex. With the less coordinating P5 group, reactions are possible, but photochemical activation is necessary. The silylene, which is the expected decomposition product, can be trapped, either with alcohols or dienes, but any attempt to characterize the base-stabilized silylene was unsuccessful.
Conclusion We have developed a new approach to Lewis basestabilized silanediyl- transition metal complexes, based on the photochemical reaction of 16-e- transition metal carbonyl species with dihydrosilanes in the presence of either external or internal donor molecules. Trapping experiments with acetylenes, dienes, and alcohols emphasize the efficiency of the silanediyl- transition metal complexes as silylene sources. The reactivity of these complexes is inversely proportional to their stability: the more coordinated the Lewis base adducts, the less reactive they are. Experimental Section All manipulations were carried out under an atmosphere of dry argon. Air-sensitive reagents and products were handled by standard Schlenk techniques. All solvents were dried and distilled from purple solutions of sodiumhenzophenone or P205. Commercially available chemicals were used as such without any further purification. The synthesis of starting dihydrosilanes has been described20in the literature. 29Si,I3C, 'H, and 31PNMR spectra were recorded on a Bruker WF'200 SY or AC 250 spectrometer. 'H and chemical shifts were measured against Me& using solvent resonances as standard locks. 29Sichemical shifts were referenced to external Mersi in the same solvent. IR spectra were recorded on a Perkin-Elmer 1600 FT instrument as KBr pellets, Nujol suspensions, or solutions in CaF2 cells. The mass spectra were obtained on a JEOL JMS DlOO apparatus by E1 ionization a t 70 or 30 eV. Elemental analyses were carried out by the Service Central de Microanalyse du CNRS or ENSC Montpellier. All photochemical reactions were performed a t room temperature by use of an immersed Hanovia 450-W mediumpressure mercury lamp in a quartz reaction vessel under argon. (CsHa)z(DMI)Si=Fe(C0)4. (Diphenylsilanediyl)iron(O) Tetracarbonyl-l,3-dimethyl-2-imidazolidinone (3). A solution of diphenylsilane l (3.69 g, 20 mmol) and 1,3-dimethyl24midazolidinone (2.28 g, 20 mmol) in 350 mL of pentane was transferred into a 500-mL quartz reaction vessel. Iron pentacarbonyl(2.62 mL, 20 mmol) was added to this solution, and the mixture was irradiated a t room temperature. Separation of a black-red sticky solid started takiEg place after 20 min of irradiation. Complete disappearancs of v(SiH), in the IR spectrum, was observed after 5 11. Pentane solution was removed from the reaction vessel, and the remaining solid 3 was washed with pentane and analyzed. Yield: 93%. Synthesis of 3 from p(Diphenylsilanediy1)iron Tetracarbonyl(2). Freshly prepared p(diphenylsilanediy1)iron tetracarbonyl complex7 (2;0.35 g, 5 mmol) was dissolved in (1.14 350 mL of toluene, and 1,3-dimethyl-2-imidazolidinone g, 10 mmol) was injected dropwise to this solution. The ( 2 3 ) ( a ) Carre, F. H.; Corriu, R. J. P.; Lanneau, G. F.; Yu, 2. Organometallics 1991,10,1236. (b)Corriu, R. J. P.; Royo, G.; de Saxce, A. J . Chem. SOC.,Chem. Commun. 1980,892.( c ) Arya, P.; Corriu, R. J. P.; Gupta, K.; Lanneau, G. F.; Yu, 2. J . Organomet. Chem. 1990, 399, 11. (d) Corriu, R. J. P ; Lanneau, G. F.; Yu, 2. Tetrahedron 1993, 49, 9019.
Organometallics, Vol. 14,No. 4, 1995 1663 resulting mixture was irradiated for 1 h. Evaporation of solvent furnished complex 3 in 90% yield. Anal. Caicd for C2lH2oN20&3iFe: C, 54.31; H, 4.31; N, 6.03. Found: C, 54.48; H, 4.49; N, 6.12. 'H NMR (CDC13): d 4.18 (br s, 6H, 2NCH3), 6.18 (s,4H, 2NCH2),7.01-7.98 (m, 10H, ArH) [uncoordinated DMI: 'H NMR (CDC13) 6 2.70 (s, 6H, 2NCH31, 3.25 (s, 4H, 2NCHz)l. 13C NMR (CDC13): 6 28.63 (NCHs), 48.12 (NCH2) 125.35-143.44 (aromatics), 161.6 (>C=O), 217.6 (CO), MS [EI, 70 eV; m l e (relative intensity %)I: 437 (M+ - CO, 1001, 396 (0.6), 361 (181,317 (10)182 (15), 154 (101,114 (60). 29SiNMR (toluenelCsD6): d +91.30. IR (CDC13, cm-'): v(>C=O, CO), 1688 (>C=O), 2019, 1995 ((20). (Cfi&HMPASi=Fe(CO)4. (Diphenylsilanediy1)iron( 0 ) Tetracarbonyl Hexamethylphosphorictriamide (4). The preparation of 4 was done analogously to the synthesis of complex 3. Complex 4 was crystallized from CHC1&7Hs (40l60) mixture a t -15 "C. mp: 121-122 "C. Yield: 43% Anal. Calcd for CzzHzsN305PSiFe: C, 49.90; H, 5.29. Found: C, 49.98; H, 5.39. 'H NMR (CDC13): d 2.52 (d, CH3, 18H), 7.33, 7.69 (m, aromatics, 10H). 13C NMR (CDC13): 6 37.22 (NCHs), 127.72, 128.18, 129.17, 130.83, 135.05, 143.56 (aromatics), 217.62 (CO). 29SiNMR (CDC13): 6 +79.52 [d, 2J(31P29Si) = 23.86 Hzl. 31P-NMR(CDC13): d +25. IR (CDC13, cm-'1: v(CO), 2017, 1932, 1885. MS [EI, 30 eV; mle (relative intensity %)I: 529 (M+, 15), 501 (-CO, 10) 473 (141,445 (351, 417 (501, 360 (201, 322 (401, 314 (101, 266 (40), 236 (1001, 182 (80), 135 (go), 119 (201, 92 (70), 56 (45). [2-(Me2NCHz)CsH41CsHaSi=Fe(CO)r. [S-[(Dimethylamino)methyl]phenyl]phenylsilanediyliron(O) Tetracarbonyl (5a). In a 500-mL quartz reaction vessel, [2-[(dimethylamino)methyllphenyllphenyldihydrosilane (4a; 2.41 g, 10 mmol) was dissolved in 350 mL of pentane. To this colorless solution was added iron pentacarbonyl(1.31mL, 10 mmol) by a syringe. This mixture was irradiated at room temperature for 5-6 h. A red solid started precipitating after 15 min. The progress of the reaction was monitored by IR. After complete disappearance of silane 4a, pentane was removed with a cannula and solid 5a was washed three times with pentane and isolated as a powder. mp: 130 "C dec. Yield: 3.25 g (80%). Anal. Calcd for C19H17NSiFe04: C, 56.0; H, 4.2; N, 3.4; Si, 6.7. Found: C, 56.03; H, 4.32; N, 3.54; Si. 6.61. 29Si NMR (CDC13, 22 "C): 6 +118. 'H NMR (CDC13): 6 1.85 (s, 3H, NCHa), 2.18 (s, 3H, NCH3), 2.65,2.73, 3.39, 3.47 [dd, 2H, AB system, 2J(1H'H)= 14.3 Hz, NCH21, 6.65, 6.86, 7.11, 7.48, 7.82 (9H, aromatics). I3C NMR (CDC13): 6 47.73 (NCH3),49.57 (NCH3), 68.60 (NCH21, 123.73, 130.56, 136.52, 138.40. 139.34 (aromatics),215.62 (CO). IR (CDC13,cm-'): v(C0) 1985, 1953, 1914, 1893. MS [EI, 70 eV; mle (relative intensity %)j: 407 (M+, 15), 779 (241, 323 (651, 295 (1001, 238 (261, 134 (261, 91 (28). [2-(MezNCHz)C&12Si=Fe(C0)4. Bis[2-[(dimethylamino)methyl]phenyl]silanediyliron(O) Tetracarbonyl(5b). Bis[2-[(dimethylamino)methyl]phenyl]dihydrosilane(4b;2.98 g, 10 mmol) was diluted in 350 mL of pentane in a 500-1nL quartz reaction vessel. Iron pentacarbnnyl(1.31mL, 10 mmol) was added with a syringe. The yellow mixture was subjected t o irradiation for 5 h a t room temperature. A red-brown solid started precipitating after 15 min of irradiation. After complete disappearance of silane (monitored by IR), the pentane solution was removed from the vessel with a cannula and the remaining solid was washed two times with pentane. This solid was further purified by crystallization in a chloroform/ toluene (80l20) mixture. Yield: 65%. Anal. Calcd for CrdI;4N204SiFe: C, 56.89; H, 5.17; N, 6.03. Found: C, 66.8G; H, 5.20; N, 6.09. 29SiNMR (CDCl3): 6 +115. NMR (CDCl?): 6 45.90 (NCH3),64.28 (NCHd. 126.47, 127.90, 130.26. 131.17, 136.22, 145.12, (CsH4),216.61 (CO). IR (CDC13,cm-'). v(C0) 1998 (br), 1889. MS LEI, 70 eV; m l e (relative intensity %)I: 408 (-2C0, 21), 380 (251, 352 (381,309 (271, 296 ( I O ) , 238 ( 8 ) , 135(40),91 (1001, 55 (40). [2-(MezNCHz)C~H4lCeH~Si=MnMeCpoz. [2-[(Dimethylamino)methyl]phenyl]phenylsilanediyl~~5-methyl-
Chauhan et al.
1664 Organometallics, Vol. 14, No. 4, 1995
pentacarbonyl(O.35 g, 1.8 mmol) diluted in 5 mL of THF was cyclopentadieny1)manganeseDicarbonyl(6a). mp: 133added dropwise to the stirred solution of silane. The mixture 134 "C. Yield: 63%. Anal. Calcd for C23H24NSiMn02: C, turned brown-red. After 1 h of stirring, THF was evaporated 64.33; H, 5.59; N, 3.26. Found: C, 64.38; H, 5.61; N, 3.29. and the resulting solid was washed three times with pentane 29Si NMR (CDC13,22 "C): d +145. 13C-NMR (CDC13): 6 22.9 and crystallized in acetone. Yield: 75%. (Cp-CHs),46.1 (NCHs),50.06 (NCHB),68.0 (NCHz),82.7, 83.1 (2)Synthesis by Photoirradiation In a 500-mL photo(Cp), 98.7 (C-CH3), 123.61, 130.23, 136.82, 138.50, 139.28 chemical reactor, [8-[(dimethylamino)methyllnaphthyll-l-phe(aromatics), 235.0,237.7 (CO). IR (CDC13, cm-I): v(C0) 1896, nyldihydrosilane (12a;3.0 g, 10.3 mmol) was dissolved in 350 1821. MS [EI, 70 eV; mle (relative intensity %)I: 429 (M+, mL of pentane. Iron pentacarbonyl (2.01 g, 10.3 mmol) was lo), 373 (18),238 (61,218 (241, 162 (271, 134 (100),91(12),52 added with a syringe. This yellow mixture was irradiated at (44). room temperature for 5 h under a constant flow of argon. The [2-(MezNCH~)CsH41~Si=Mncp(Co)z. Bis[2-[(dimethyprogress of the reaction was monitored by IR. After 15 min lamino)methyllphenylsilanediyl(~5-cyclopentadienyl~- of irradiation, a brown-red solid started precipitating. After manganese Dicarbonyl (6b). The same procedure and complete disappearance of the silane, the pentane solution was stoichiometric quantities of reactants as in case of complex 6a removed and the solid was washed with pentane and crystalwere used. The precipitated brown solid was washed with lized from acetone. Yield: 61%. The same procedure and pentane and analyzed. mp: 139-141 "C dec. Yield: 68%. molar quantities were used for the synthesis of complexes Anal. Calcd for C25H~sN202SiMn:C, 63.55; H, 6.14; N, 5.93. 14-16. mp: 140-141 "C. Anal. Calcd for C23H19NSiFe04: Found: C, 63.25; H, 6.04; N, 5.98. 29SiNMR (CDC13): d +147. C, 60.4; H, 4.2; N, 3.1; Si, 6.1. Found: C, 59.97; H, 4.60; N, 13CNMR(CDC13): d 47.85 (NCH3),67.42(NCH2),83.44(CsH5), NMR (CDCl3): 3.25; Si, 5.97. 29SiNMR (CDC13): d +101. 127.64, 129.36, 132.76, 133.68, 136.63, 144.86 (aromatics), b 50.39 (NCHs), 51.40 (NCHs), 68.30 (NCHz), 125.1-139.6 234.67,235.49 (CO). IR (CDC13, cm-'): v(C0) 1893, 1821. MS (aromatics), 217 (CO). IR (CC14, cm-l): v(C0) 1978, 1951, [EI, 70 eV; mle (relative intensity %)I: 445 (-CO, 201, 416 1911, 1896. MS [EI, 70 eV; mle (relative intensity %)I: 457 (351,402 (281,354 (20),296 (lo), 238 (101, 135 (42),91(80),55 (M+,5) 429 (9), 373 (201, 345 (30), 302 (121, 278 (81, 244 (141, 215 (181, 185 (431, 167 (201, 141 (801, 55 (100). (100). [8-(MezN)CloHs]-l-CsHaSi=Fe(CO)4. [&[(Dimethylami[2-(MezNCHz)CsH41CsSi=Mo(CO)a. [B[(DimethylamiTetracarbonyl no)]naphthyl] 1-phenylsilanediyliron(O) no)methyl]phenyl]phenylsilanediylmolybdenum(O) Pen(14). Yield: 56%. Anal. Calcd for C22H17NSiFe04: C, 59.59; tacarbonyl (7a). Yellow sticky solid. Yield: 48%. Anal. H, 3.83; N, 3.16; Si, 6.32. Found: C, 59.61; H, 3.86; N, 3.14; Calcd for C20H17NSiMo05: C, 50.52; H 3.57; N 2.94. Found: Si, 6.30. 29SiNMR (CDC13): d +126. 13C NMR (CDC13, 22 C, 50.61; H, 3.59; N, 2.98. 'H NMR (CDC13): unresolved "C): d 46.9 (NCH3), 48.2 (NCH3), 122.1-138.2 (aromatics), material. 29SiNMR (CDC13): b +111. 13C NMR (CDC13, 22 215.0 (CO). IR (CDC13, cm-l): v(C0) 1977, 1954, 1914, 1894. "C): d 47.4 (NCH3), 50.1 (NCHs),68.1 (NCHz), 123.63, 130.52, MS [EI, 70 eV; mle (relative intensity %)I: 443 (M+, 91, 415 136.51, 138.42, 139.34 (aromatics), 210.4, 212.56 (CO). IR (121, 359 (61, 331 (B), 276 (291, 26 (301, 200 (48), 185 (43), 168 (CDC13, cm-'1: v(C0) 2055 (fine), 1926 (very large). (221, 84 (loo), 53 (57). [~-(M~~NCHZ)C~H~]C~H~S~=C~(CO)~. [S-[(Dimethylami[8-(MezNCHz)CloHe]-l-CsH5Si=MnMeCp(CO)~. [8-[(Dino)methyl]phenyl]pheiiylsilanediylchromium(0) Penmethylamino)methyllnaphthyll-l-phenylsilanediyl~~6tacarbonyl (8). The same procedure as above and stoichiomethylcyclopentadieny1)manganeseDicarbonyl (Ma). metric quantities of reactants were used. The resulting yellow mp: 230-231 "C. Yield: 45%. Anal. Calcd for C27H26solid was washed three times with pentane and analyzed. NSiMnO2: C, 67.64; H, 5.43; N, 2.92; Si, 5.84. Found: C, mp: 171-172 "C (lit.Iomp 171 "C). Yield: 68%. Anal. Calcd 67.50; H, 5.52; N, 3.09; Si, 5.15. 29SiNMR (CDC13): d +124 . for CzoH17NSiCrOs: C, 55.68; H, 3.97; N, 3.25. Found: C, NMR (CDC13): d 14.6 (Cp*CH3),45.0 (NCHB),48.0 (NCHs), 55.56; H, 3.61; N, 3.21. 29SiNMR (CDC13, 22 "C): 6 +122. 'H 65.9 (NCH2) 85.5 , 82.8 (C5H5), 103.1 (C*CH3), 121.6-136.2 NMR (CDC13,22 "C): 6 1.86 (s, 3H, NCH3),2.12 (s, 3H, NCH31, (aromatics), 234.1,237.0 (CO). IR (CDC13, cm-'1: v(C0) 1897, 2.63,2.71,3.32, 3.40 [dd, 2H, AB system, 2J(1H1H)= 14.01 Hz, 1822. MS [EI, 70eV; mle (relative intensity %)I: 479 (M+, NMR NCHz], 6.06, 6.93, 7.08, 7.51, 7.92 (9H, aromatics). 181,423 (811, 288 (21), 245 (621, 215 (301, 184 (311, 134 (1001, (CDC13, 22 "C): b 47.29 (NCHz),48.63 (NCHs), 68.17 (NCHz), 79 (62), 55 (81). 123.81, 128.83, 129.74, 134.60, 139.08, 142.81 (aromatics), [ ~ - ( M ~ ~ N C H ~ ) C ~ O H ~ ~ - ~ - C I ~ I ,[8-[(DiS~=M~M~C~(C 221.33, 224.85 ((20).IR (CDC13, cm-'1: v(CO), 2055 (fine), methylamino)methyl]naphthyll-l-naphthylsilanediyl(qs1926 (very large). MS [EI, 70 eV; mle (relative intensity %)I: methylcyclopentadieny1)manganese Dicarbonyl (15b). mp (powder): 249-250 "C. Yield: 40%. Anal. Calcd for 431 (M+, 81, 403 (101, 347 (22), 319 (151, 291 (1001, 238 (151, C22HzsN305PSiFe: C, 49.90; H, 5.29; N, 7.93. Found C, 49.98; 134 (301, 91 (25). H, 5.39; N, 8.01. The IH NMR (CDC13)spectrum of the brown [~-[(M~~NCHZ)C~H~]C&S~=F~(CO)~. [2-[(Dimethylamisolution gives only broad signals in the expected region, even no)methyllphenyllmethylsilanediyliron(0)Tetracarbonyl(10). [2-[(Dimethylamino)methyllphenyllmethyldihydro- changing the probe temperature (two peaks a t about 2-3 ppm) 29SiNMR (CDC13): 6 +127. 13C NMR (CDCl3): d 15.0 silane (9; 0.35 g, 2 mmol) was dissolved in 15 mL of THF, and (CPCH~), 45.01 (NCH3), 47.5 (NCH3I, 67.5 (NCHz), 81.9 , 83.1 iron pentacarbonyl(O.26 mL, 2 mmol) diluted in 5 mL of THF (CbHb), 99.7 (C*CH3), 125.3-141.7 (aromatics) 235,237.4 (CO). was added dropwise to this solution. This mixture was stirred IR (CDC13, cm-I): v(C0) 1892, 1818. MS [EI, 70 eV; mle for a further 2 h a t room temperature. Removal of solvent (relative intensity a ) ] : 529 (M+, 6), 473 (371, 338 (191, 295 under vacuum furnished a red-brown solid which was washed (18),265 (101, 185 (421, 141 (loo), 115 (321, 55 (97). with pentane and analyzed. Yield: 72%. Anal. Calcd for c14[~-(M~~NCHZ)C,~H~]-~-C~H~S~-M~C~(CO)Z. [8-[(DimeH15NSiFe04: C, 48.69; H, 4.34; N, 4.05. Found: C, 48.70; H, thylamino)methyl]naphthyll-l-phenylsilanediyl(~64.35; N, 4.01. 29SiNMR (CDC13, 22 "C): d +123.6. NMR cyclopentadieny1)manganese dicarbonyl(16). mp (pow(CDC13): b 5.0 (SiCH3),46.1 (NCHz), 48.2 (NCH3),66.8 (NCH2), der): 226-227 "C. Yield 62%. Anal. Calcd for C26H23NSiMn121-135 (aromatics), 214.5 ((20). IR (CDC13,cm-I): v(C0) 0 2 : C, 67.24; H, 4.95; N, 3.01. Found: C, 67.18; H, 4.83; N, 2040, 1945, 1905, 1890. 3.08. IH NMR (CDC13): unresolved material. 29Si NMR [8-(MezNCH~)CloHsl-l-CsHsSi=Fe(CO)r. [&[(Dimethy(CDC13): 6 +125.2. 13C NMR (CDC13): d 48.1 (NCH31, 49.4 lamino~methyllnaphthyll-l-phenylsilanediyliron(O) Tet(NCH3),65.9 (NCH2)81.19 (C5H5),124.62-142.46 (aromatics), racarbonyl(13). (1)Synthesis in THF. [%[(Dimethylami234.13,236.34 (CO). IR (CDC13, cm-'): v(C0) 1888, 1821. MS no)methyllnaphthyll-1-phenyldihydrosilane(lla;0.52 g, 1.8 [EI, 70 eV; mle (relative intensity %)I: 464 (M+,111,408 (201, mmol) was diluted in 15 mL of THF a t room temperature. Iron 288 (151,245 (281,215 (181,184 (26),141 (45), 79 (53),55(100).
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Divalent Silicon-Transition Metal Complexes
Organometallics, Vol. 14,No.4,1995 1665
Table 3. Summary of Crystal Data and Details of Intensity Photolysis of Complex 5a with Diphenylacetylene. Collection for 5a The freshly prepared complex 5a (4.01g, O.Olmo1) was diluted in 350 mL of toluene followed by addition of diphenylacetylene Crystal Data (8.90 g, 0.05 mol, diluted in 50 mL of toluene) and irradiated formula C 19H 17FeOdSi fw 407.3 at 22 "C. The reaction progress was monitored by IR and TLC. cryst syst triclinic The total irradiation time was 6 h. The solvent was stripped space group P 1 (No. 2) off and the crude mixture was chromatographed on a Florisil a, A 8.284(2) column (33 x 2 cm). Elution with pentane furnished unreacted h, A 8.404(2) diphenylacetylene as the first fraction. A yellowish sticky solid c, A I3.497(3) [2-[~dimethylamino~methyllphenyllphenylsilacyclopent-2,4-di- a, deg 97.02( 1) ene2' 17 was obtained as the second fraction with pentane/ /L deg 93.68( I ) ether (80/20). Further washing of the column with ether gave Y,deg 91.25( I ) cell VOI, A' 930.3 tetraphenylcyclobutadieneiron tricarbonyl complex 18. 2 dcalcd?g 2; 1.598 [2-[(Dimethylamino)methyllphenyllphenylsilaF(000) 968 cyclopent-2,4 diene (17). Anal. Calcd for C43H37NSi: C, 0.75 x 0.48 x 0.20 cryst size, mm 86.72; H, 6.21; N, 2.35. Found: C, 86.05; H, 6.32; N, 2.56. cryst color and habit colorless plates 29Si NMR (CDC13): 6 -14.85. I3C NMR (CDC13): 6 44.01 Data Collection and Data Reduction (NCH3), 64.83 (NCHz), 125.2-135.8 (aromatics, C=C). 'H diffractometer Enraf-Nonius CAD4 NMR (CDC13): 6 1.52 (s, 6H, NCHs), 2.61 (s, 2H, NCH2) 6.8Mo K a (1= 0.710 73 A) radiation 7.92 (m, 29H, aromatics). MS [EI, 70 eV, m / e (relative 193 3 temp, K intensity %)I: 580 (M+ -CH3, 81, 551 (91, 538 (61, 505 (121, scan type w-scan 461 (3), 289 (51, 256 (251, 240 (18),211 (211, 191 (8),178 (81, 0.75 + 0.30 tan 0 scan range, deg 165 (211, 134 (171, 105 (231, 91 (351, 77 (161, 58 (100). \ariah!e; max 60 scan time, s Photolysis of Complex 5a in the Presence of 2,320 limits, deg; octants 4.0-50.0; &h,+k,f[ reflections collected 3488 Dimethylbutadiene. A 10-fold excess of 2,3-dimethylbutano. of reflns for p-scans 9 diene (8.25 g, 0.1 mol) was injected into a 350-mL toluene m (Mo Ka).cm-I 8.9 solution of freshly prepared complex 5a (4.01 g, 0.01 mol). This min/max transm factor 0.988/1.000 mixture was irradiated a t room temperature for 6 h. Toluene no cryst decay, R was evaporated and resulting mixture was chromatographed Solution and Refinement on a Florisil column (33 x 2 cm). [2-[(Dimethylamino)methyllno. of independent data 3171 phenyl~phenyl-3,4-dimethylsilacyclopent-2-ene (19)was isono. of observed data 3171 ( I 0.00) lated in pentane/ether (90/10) as the first fraction. The second no. of refined params 303 fraction contained 2,3-dimethylbutadieneirontetracarbonyl Rmerge 0.009 (Fo) complex 20. Fe3(C0)12was also isolated in trace amounts as R"" indexes (all data) R = 0.027, RW = 0.030 the third fraction in ether. GOF; p 0.6377, 0.00 19. Yield: 42%. Anal. Calcd for C21H27SiN: C, 78.50; H, maxhin peak final diff map, e 0.55/-0.29 max shifuerr 0.0) were used in the refinement. The structure has been solved by direct methods and subsequent full-matrix least-squares refinement cycles and difference Fourier syntheses. All atoms are refined with anisotropic displacement parameters. Hydrogen atoms could be located and were freely refined. Refinement minimized the function Li~(lF~l - IFC1l2, where w = 11u2and converged yielding Rw = 0.030. Residual electron density maxima and minima were 0.55 and -0.29 e A-3. Crystal data and details of data collection are given in Table 3. Atomic coordinates are listed in Table 4. All calculations were performed on a MicroVAX 3100 computer using standard programs.25
Acknowledgment. Helpful corrections of the English by Dr. W. Douglas were greatly appreciated. SupplementaryMaterial Available: A description of the X-ray single crystal structure determination, including tables of crystal data, data collection, and solution and refinement parameters, atomic coordinates, bond distances and angles, and the thermal parameters (12 pages). Ordering information is given on any current masthead page. OM940854Q (25)Scherer, W.; Kiprof, P.; Herdtweck, E.; Schmidt, R. E.; Birkhahn, M.; Massa, W. STRUX-N; A Program System to Handle X-ray Data; TU Munchen und University Marburg, Marburg, Germany, 1985/1987/ 1994 (includes the programs Multan 11/82,Ortep 11, Platon, Schakal, and SDP).
