Synthesis, Structure, and Reactivity of Polymetallic C3OMe Complexes of the Formula (5-C5Me5
详细信息 查看全文
- 作者：Stephen B. Falloon ; Weiqing Weng ; Atta M. Arif ; and J. A. Gladysz
- 刊名：Organometallics
- 出版年：1997
- 出版时间：May 13, 1997
- 年：1997
- 卷：16
- 期：10
- 页码：2008 - 2015
- 全文大小：243K
- 年卷期：v.16,no.10(May 13, 1997)
- ISSN：1520-6041
文摘
Reaction of(
5-C5Me5)Re(NO)(PPh3)(C
CLi)with Re2(CO)10 and thenMe3O+BF4-givesthe trirhenium C3OMe complexcis-(5-C5Me5)Re(NO)(PPh3)(CCC(OMe)=)Re(CO)4Re(CO)5(3, 92%). An analogous reaction withOs3(CO)12 gives heterotetrametallic(5-C5Me5)Re(NO)(PPh3)(CCC(OMe)=)Os3(CO)11(4, 87%). NMR, IR, and crystallographic data(4) showsubstantial contributions by+Re=C=C=C(OMe)-M-resonance forms. Reaction of 3 andexcess BF3 gas in toluene precipitates[(5-C5Me5)Re(NO)(PPh3)(
-1:3:1-CCC)(Re(CO)4)Re(CO)5]+BF4-(5, 64%). A crystal structure shows a slightly bentC3 moiety (152(4)
) thatbinds a rhenium on each end and spans a third. NMR, IR, and bondlength data show that5 is best viewed as a completely metalated 
propargyl orPRe=CC C -Re(CO)5 adductofRe(CO)4. It is likely derived by initialmethoxide abstraction from 3 to give aReCCCReRespecies, followed by rearrangement. Reaction of(5-C5Me5)Re(NO)(PPh3)(CCCCLi)withRe2(CO)10 and thenMe3O+BF4-gives the C5OMe complexcis-(5-C5Me5)Re(NO)(PPh3)(CCCCC(OMe)=)Re(CO)4Re(CO)5(8, 44%). When 4 or 8 aretreated with BF3 gas,Cxcomplexes are not detected.
5-C5Me5)Re(NO)(PPh3)(CCLi)with Re2(CO)10 and thenMe3O+BF4-givesthe trirhenium C3OMe complexcis-(5-C5Me5)Re(NO)(PPh3)(CCC(OMe)=)Re(CO)4Re(CO)5(3, 92%). An analogous reaction withOs3(CO)12 gives heterotetrametallic(5-C5Me5)Re(NO)(PPh3)(CCC(OMe)=)Os3(CO)11(4, 87%). NMR, IR, and crystallographic data(4) showsubstantial contributions by+Re=C=C=C(OMe)-M-resonance forms. Reaction of 3 andexcess BF3 gas in toluene precipitates[(5-C5Me5)Re(NO)(PPh3)(-1:3:1-CCC)(Re(CO)4)Re(CO)5]+BF4-(5, 64%). A crystal structure shows a slightly bentC3 moiety (152(4)) thatbinds a rhenium on each end and spans a third. NMR, IR, and bondlength data show that5 is best viewed as a completely metalated propargyl orPRe=5-C5Me5)Re(NO)(PPh3)(CCCCLi)withRe2(CO)10 and thenMe3O+BF4-gives the C5OMe complexcis-(5-C5Me5)Re(NO)(PPh3)(CCCCC(OMe)=)Re(CO)4Re(CO)5(8, 44%). When 4 or 8 aretreated with BF3 gas,Cxcomplexes are not detected.