Si-H Bond Activation by (Ph3P)2Pt(2-C2H4) in Dihydrosilicon Tricycles that Also
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- 作者：Janet Braddock-Wilking ; Joyce Y. Corey ; Lisa M. French ; Eunwoo Choi ; Victoria J. Speedie ; Michael F. Rutherford ; Shu Yao ; Huan Xu ; Nigam P. Rath
- 刊名：Organometallics
- 出版年：2006
- 出版时间：July 31, 2006
- 年：2006
- 卷：25
- 期：16
- 页码：3974 - 3988
- 全文大小：411K
- 年卷期：v.25,no.16(July 31, 2006)
- ISSN：1520-6041
文摘
Several tricyclic phenoxasilin and phenazasiline heterocycles were synthesized from the corresponding2,2'-dilithio-diphenyl ether or diphenyl amine precursor and silicon tetrachloride (or trichlorosilane)followed by reduction with lithium aluminum hydride [H2SiAr2: Ar2 = C12H8O (1); Ar2 = C14H12O (2);Ar2 = C13H11N (3); Ar2 = C15H15N (4); Ar2 = C13H9Br2N (5)]. The reactivity of hydrosilanes 1-5 with(Ph3P)2Pt(
2-C2H4) (6) was investigated. At room temperature, mononuclear complexes, (Ph3P)2Pt(H)(SiAr2H) and (Ph3P)2Pt(SiAr2H)2, were generally observed by NMR spectroscopy but were too reactiveor unstable to isolate. Dinuclear and in some cases trinuclear Pt-Si-containing complexes were observedas the major products from the reactions. Symmetrical dinuclear complexes, [(Ph3P)Pt(
-2-H-SiAr2)]2(8 and 22, respectively), were produced from the reaction of 1 or 3 with 6. In contrast, reaction of silane2 with 6 produced a trinuclear complex, [(Ph3P)Pt(-SiAr2)]3 (16), as the major product. However, reactionof 4 or 5 with complex 6 produced an unsymmetrical dinuclear complex, [(Ph3P)2Pt(H)(-SiAr2)(-2-H-SiAr2)Pt(PPh3)] (26 and 30, respectively), as the major component. The molecular structures of asymmetrical (22) and unsymmetrical dinuclear (30) complex as well as a trinuclear (16) complex weredetermined by X-ray crystallography.
2-C2H4) (6) was investigated. At room temperature, mononuclear complexes, (Ph3P)2Pt(H)(SiAr2H) and (Ph3P)2Pt(SiAr2H)2, were generally observed by NMR spectroscopy but were too reactiveor unstable to isolate. Dinuclear and in some cases trinuclear Pt-Si-containing complexes were observedas the major products from the reactions. Symmetrical dinuclear complexes, [(Ph3P)Pt(-2-H-SiAr2)]2(8 and 22, respectively), were produced from the reaction of 1 or 3 with 6. In contrast, reaction of silane2 with 6 produced a trinuclear complex, [(Ph3P)Pt(-SiAr2)]3 (16), as the major product. However, reactionof 4 or 5 with complex 6 produced an unsymmetrical dinuclear complex, [(Ph3P)2Pt(H)(-SiAr2)(-2-H-SiAr2)Pt(PPh3)] (26 and 30, respectively), as the major component. The molecular structures of asymmetrical (22) and unsymmetrical dinuclear (30) complex as well as a trinuclear (16) complex weredetermined by X-ray crystallography.