Synthesis and structures of silicon-, germanium-, and tin-containing tungsten carbyne complexes (ButO)3W C—EPh3and [(ButO)3W≡C]2EPh2(E = Si, Ge, Sn)

Safronova, A. V.; Bochkarev, L. N.; Stolyarova, N. E.; Chemistry, Russian Academy of Sciences O. A. LukyanovN.D. Zelinsky Institute of Organic; Malysheva, I. P.; Basova, G. V.; Fukin, Georgy K.; Kurskii, Yu. A.; Khorshev, S. Ya.; Abakumov, G. A.

doi:10.1023/b:rucb.0000011869.83994.94

Cited by 12 publications

(12 citation statements)

References 8 publications

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“…Selected structural data for published silylcarbynes are given in Table S1 in the Supporting Information alongside those for the new complexes described herein. The tungsten atom in 3b displays a distorted-octahedral coordination with the two axial positions occupied by a bromide ligand (W–Br = 2.6899(5) Å) and the carbyne carbon (WC = 1.824(4) Å).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of a Stable Methylidyne Complex

2015

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The successive treatment of [W(CO) 6 ] with LiSiPh 3 , (OCBr) 2 , and 4-picoline (pic) affords the silylcarbyne complex [W(CSiPh 3 )Br(CO) 2 (pic) 2 ], which reacts with 1,2-bis(dicyclohexylphoshino)ethane (dcpe), 1,2-bis-(diphenylphosphino)ethane (dppe), and tetramethylethylenediamine (tmeda) to provide the complexes [W(CSiPh 3 )Br(CO) 2 (L 2 )] (L 2 = dcpe, dppe, tmeda). Fluoride-mediated protodesilylation of [W(CSiPh 3 )Br(CO) 2 (dcpe)] with moist [Bu 4 N]F provides the stable and structurally characterized terminal methylidyne complex [W(CH)Br(CO) 2 (dcpe)] (shown) in addition to traces of the ethene-1,2-diylidyne complex {Br(dcpe)(CO) 2 W} 2 (μ-CCHCHC).

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Section: Resultsmentioning

confidence: 99%

Synthesis of a Stable Methylidyne Complex

2015

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“…X ray diffraction study demonstrated that complexes 1 and 2 (Figs 1 and 2, respectively) are structurally simi lar to the tert butoxy containing carbyne complexes Ph 3 EC≡W(OBu t ) 3 (E = Ge or Sn) studied earlier. 8 The tungsten and germanium atoms in complexes 1 and 2 have a distorted tetrahedral coordination. The Ph and CH 2 Bu t substituents in molecule 1 are in a staggered con formation with respect to each other, which minimizes their mutual repulsion.…”

Section: Methodsmentioning

confidence: 99%

“…The influence of the nature of the substituent R bound to the carbyne carbon atom is much less well known. Recently, 7, 8 we have synthesized the tungsten carbyne complexes Ph 3 EC≡W(OBu t ) 3 and Ph 2 E[C≡W(OBu t ) 3 ] 2 (E = Si, Ge, or Sn) containing organosilicon, germanium, and tin substituents at the carbyne carbon atom. The resulting carbyne complexes exhibit high catalytic activity in metathesis of hept 3 yne (as a test substrate).…”

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Synthesis and structures of germanium-containing tungsten carbyne complexes Ph3gec≡w(ch2but)3 and Ph3GeC≡W(CH2SiMe3)3

et al. 2006

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New germanium containing tungsten carbyne complexes Ph 3 GeC≡W(CH 2 R) 3 (R = Bu t or SiMe 3 ) were synthesized by the reaction of the alkoxy derivative Ph 3 GeC≡W(OBu t ) 3 with alkyllithium reagents RCH 2 Li. The new compounds were isolated in individual form as crystals in 95 and 90% yields, respectively, and were characterized by elemental analysis, 1 H and 13 C NMR spectroscopy, and X ray diffraction. X ray diffraction study showed that the coordination environment of the W and Ge atoms in the Ph 3 GeC≡W(CH 2 Bu t ) 3 and Ph 3 GeC≡W(CH 2 SiMe 3 ) 3 complexes can be described as a distorted tetrahedron.Nowadays, olefin metathesis catalyzed by transition metal carbene complexes is widely used in organic syn thesis. 1-6 Metathesis of acetylenic hydrocarbons medi ated by transition metal carbyne complexes is much less well studied and is used to a lesser extent. 4-6 The tung sten carbyne complexes RC≡W(OR´) 3 (R and R´ = Alkyl or Aryl) are most efficient catalysts for metathesis of acety lenic hydrocarbons. 4 The catalytic activity of complexes was found 4 to be to a large extent determined by the nature of alkoxy groups. The influence of the nature of the substituent R bound to the carbyne carbon atom is much less well known. Recently, 7,8 we have synthesized the tungsten carbyne complexes Ph 3 EC≡W(OBu t ) 3 and Ph 2 E[C≡W(OBu t ) 3 ] 2 (E = Si, Ge, or Sn) containing organosilicon, germanium, and tin substituents at the carbyne carbon atom. The resulting carbyne complexes exhibit high catalytic activity in metathesis of hept 3 yne (as a test substrate). The catalytic activity of tin contain ing derivatives is substantially higher than that of silicon containing complexes, and the trinuclear complexes Ph 2 E[C≡W(OBu t ) 3 ] 2 are more efficient catalysts than the dinuclear complexes Ph 3 EC≡W(OBu t ) 3 . 9 In this connec tion, it was of interest to elucidate how the catalytic activ ity of silicon , germanium , and tin containing tungsten carbyne complexes changes when the alkoxy groups are replaced by other ligands, in particular, by alkyl groups.It is known that the tert butoxy groups in the tungsten carbyne complexes RC≡W(OBu t ) 3 (R = Alk or Ar) are readily replaced by alkyl groups in the reactions with alkyllithium compounds or Grignard reagents. 10 In the present study, we used this method for the replacement of the tert butoxy group in the germanium containing tung sten carbyne complex by the neopentyl and trimethyl silylmethyl substituents. Results and DiscussionIt was demonstrated that the tungsten triphenylgermyl carbyne complex Ph 3 GeC≡W(OBu t ) 3 (see Ref. 7) readily reacts with neopentyllithium and trimethylsilylmethyl lithium to give new alkyl containing carbyne complexes Ph 3 GeC≡W(CH 2 Bu t ) 3 and Ph 3 GeC≡W(CH 2 SiMe 3 ) 3 , re spectively (Scheme 1). Scheme 1Ph 3 GeC≡W(OBu t ) 3 + 3 RCH 2 Li Ph 3 GeC≡W(CH 2 R) 3 + 3Bu t OLi R = CMe 3 (1), SiMe 3 (2) Reaction conditions: diethyl ether, 0 °C.Both complexes were isolated in individual form as crystals in 95 and 90% yields, respectively. The 1 H ...

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“…The starting reagents, viz., the trinuclear organosilicon, organogermanium, and organotin containing carbyne complexes Ph 2 E[C≡W(OBu t ) 3 ] 2 (E = Si, Ge, or Sn), were synthesized according to a procedure described earlier. 11 The IR spectra were measured on a Perkin-Elmer 577 spectrometer. Samples were prepared under argon as Nujol mulls.…”

Section: Methodsmentioning

confidence: 99%

“…7, 8 The starting carbyne complexes can easily be synthesized by stoichio metric metathesis of acetylenic derivatives with dimeric tungsten alkoxide W 2 (OBu t ) 6 . 9- 11 Earlier, 12 we have found that the reactions of the organosilicon, organogermanium, and organotin contain ing carbyne complexes Ph 3 E-C≡W(OBu t ) 3 (E = Si, Ge, or Sn) with two equivalents of HCl in toluene or pentane at -78 °C afforded one equivalent of new tungsten carbene complexes Ph 3 E-CH=WCl 2 (OBu t ) 2 and one equivalent of tert butyl alcohol.…”

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Synthesis of trinuclear silicon-, germanium-, and tin-containing tungsten carbene complexes [(ButO)2(Cl)2W=CH]2EPh2 (E = Si, Ge, or Sn). Crystal structure of [(ButO)2(Cl)2W=CH]2SiPh2 complex

et al. 2005

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New trinuclear organosilicon, organogermanium, and organotin containing tungsten carbene complexes Ph 2 E[CH=WCl 2 (OBu t ) 2 ] 2 (E = Si, Ge, or Sn) were synthesized by the reaction of the trinuclear carbyne complexes Ph 2 E[C≡W(OBu t ) 3 ] 2 with HCl. The tin contain ing carbene complex is thermally unstable and was identified in solution by 1 H and 13 C NMR spectroscopy. The silicon and germanium tungsten carbene complexes were isolated in high yields as individual crystals and were characterized by elemental analysis, IR spectroscopy, and 1 H and 13 C NMR spectroscopy. The structure of the silicon containing complex Ph 2 Si[CH=WCl 2 (OBu t ) 2 ] 2 was established by X ray diffraction.Certain types of tungsten carbene complexes serve as catalysts for metathesis of olefinic hydrocarbons. 1-5 One of potential procedures for the synthesis of carbene com plexes is based on protonation of the carbyne complexes W(≡CR)(OBu t ) 3 , including those containing various func tional groups at the carbyne carbon atom. 6 The resulting carbene complexes W(=CHR)(OBu t ) 2 X 2 are inactive in olefin metathesis. However, these complexes exhibit high catalytic activity in these reactions in the presence of Lewis acids AlX 3 or GaX 3 (X = Cl or Br). 7,8 The starting carbyne complexes can easily be synthesized by stoichio metric metathesis of acetylenic derivatives with dimeric tungsten alkoxide W 2 (OBu t ) 6 . 9-11Earlier, 12 we have found that the reactions of the organosilicon, organogermanium, and organotin contain ing carbyne complexes Ph 3 E-C≡W(OBu t ) 3 (E = Si, Ge, or Sn) with two equivalents of HCl in toluene or pentane at -78 °C afforded one equivalent of new tungsten carbene complexes Ph 3 E-CH=WCl 2 (OBu t ) 2 and one equivalent of tert butyl alcohol.Subsequent studies demonstrated that the reac tion of the trinuclear tungsten carbyne complexes Ph 2 E[C≡W(OBu t ) 3 ] 2 with four equivalents of gaseous hydrogen chloride performed under analogous conditions produced new carbene complexes Ph 2 E[CH=WCl 2 (OBu t ) 2 ] 2 (E = Si (1), Ge (2), and Sn (3)) in high yields:Ph 2 E[C≡W(OBu t ) 3 ] 2 + 4 HCl → → Ph 2 E[CH=WCl 2 (OBu t ) 2 ] 2 + 2 Bu t OH E = Si (1), Ge (2), Sn (3) Reaction conditions: toluene (pentane), -78-20 °C.

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Synthesis and structures of silicon-, germanium-, and tin-containing tungsten carbyne complexes (Bu^tO)₃W C—EPh₃and [(Bu^tO)₃W≡C]₂EPh₂(E = Si, Ge, Sn)

Cited by 12 publications

References 8 publications

Synthesis of a Stable Methylidyne Complex

Synthesis of a Stable Methylidyne Complex

Synthesis and structures of germanium-containing tungsten carbyne complexes Ph3gec≡w(ch2but)3 and Ph3GeC≡W(CH2SiMe3)3

Synthesis of trinuclear silicon-, germanium-, and tin-containing tungsten carbene complexes [(ButO)2(Cl)2W=CH]2EPh2 (E = Si, Ge, or Sn). Crystal structure of [(ButO)2(Cl)2W=CH]2SiPh2 complex

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