Hydride-carbyne to carbene transformation in an osmium-acetate-bis(triisopropylphosphine) system:: Influence of the coordination mode of the carboxylate and the reaction solvent

被引：50

作者：

Bolano, Tamara ^{[1
]}

Castarlenas, Ricardo ^{[1
]}

Esteruelas, Miguel A. ^{[1
]}

Onate, Enrique ^{[1
]}

机构：

[1] Univ Zaragoza, CSIC, Inst Ciencia Mat Aragon, Dept Quim Inorgan, E-50009 Zaragoza, Spain

来源：

ORGANOMETALLICS | 2007年 / 26卷 / 08期

关键词：

D O I：

10.1021/om0611655

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The bis-solvato hydride-allenylidene complex [OsH(CCCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (1) reacts with acetic acid to give the hydride-carbyne [OsH(kappa(2)-O2CCH3)(CCHCPh2)((PPr3)-Pr-i)(2)]BF4 (2), which in 1,2-dichloroethane under reflux is stable and does not evolve into its five-coordinate carbene isomer. In acetonitrile at room temperature, complex 2 is in equilibrium with [OsH{kappa(1)-OC(O)CH3}(CCHCPh2)(CH3CN)((PPr3)-Pr-i)(2)]BF4 (4; Delta H degrees = -6.4 +/- 0.3 kcal center dot mol(-1), Delta S degrees = -22.9 +/- 1.1 eu). At 353 K, complex 4 is transformed into the carbene [Os{kappa(1)-OC(O)CH3}(CHCHCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (5; 40%), which is obtained in high yield (88%) by reaction of [Os(CHCHCPh2)(CH3CN)(3)((PPr3)-Pr-i)(2)][BF4](2) with sodium acetate in 2-propanol. The hydride-carbyne to carbene transformation is analyzed by DFT calculations.

引用

页码：2037 / 2041

页数：5

共 85 条

[71] Osmium converts terminal olefins to carbynes:: α-hydrogen migration redox isomers with reversed stability for ruthenium and for osmium [J].

Spivak, GJ ;

Coalter, JN ;

Olivan, M ;

Eisenstein, O ;

Caulton, KG .

ORGANOMETALLICS, 1998, 17 (06) :999-1001

[72] The development of L2X2Ru=CHR olefin metathesis catalysts:: An organometallic success story [J].

Trnka, TM ;

Grubbs, RH .

ACCOUNTS OF CHEMICAL RESEARCH, 2001, 34 (01) :18-29

[73] DYNAMIC SOLVENT EFFECTS ON ACTIVATED ELECTRON-TRANSFER REACTIONS - PRINCIPLES, PITFALLS, AND PROGRESS [J].

WEAVER, MJ .

CHEMICAL REVIEWS, 1992, 92 (03) :463-480

[74] Synthesis, molecular structure, and reactivity of neutral and cationic areneosmium(II) complexes with diarylcarbenes as ligands [J].

Weberndörfer, B ;

Henig, G ;

Hockless, DCR ;

Bennett, MA ;

Werner, H .

ORGANOMETALLICS, 2003, 22 (04) :744-758

[75] Vinylidene, allenylidene, and Carbyne complexes from the reactions of [OsCl2(PPh3)3] with HCCC(OH)Ph2 [J].

Wen, TB ;

Zhou, ZY ;

Lo, MF ;

Williams, ID ;

Jia, GC .

ORGANOMETALLICS, 2003, 22 (25) :5217-5225

[76] Vinylidene and carbyne complexes derived from the reactions of OsCl(PPh3)(PCP) (PCP=2,6-(PPh2CH2)2CsH3) with terminal acetylenes [J].

Wen, TB ;

Cheung, YK ;

Yao, JZ ;

Wong, WT ;

Zhou, ZY ;

Jia, GC .

ORGANOMETALLICS, 2000, 19 (19) :3803-3809

[77]

WEN TB, 2004, EUR J INORG CHEM, V2837

[78]

Werner H, 1999, EUR J INORG CHEM, P1889

[79]

Werner H, 1999, EUR J INORG CHEM, P951

[80] Carbon monoxide promoted reductive elimination of hydrogen from Tp′ platinum complexes [J].

West, NM ;

Reinartz, S ;

White, PS ;

Templeton, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (06) :2059-2066

← 1 2 3 4 5 6 7 8 9 →