Syntheses and Reactivity of Heterometallic Oxo-Acetylide Cluster Compounds. Skeletal Rearrangement and Conversion of Acetylide to Alkenyl, Alkylidene, and Allenyl Ligands on a WRe2 Framewor
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- 作者：Yun Chi ; Hsiao-Ling Wu ; Chi-Chung Chen ; Chi-Jung Su ; Shie-Ming Peng ; and Gene-Hsiang Lee
- 刊名：Organometallics
- 出版年：1997
- 出版时间：May 27, 1997
- 年：1997
- 卷：16
- 期：11
- 页码：2434 - 2442
- 全文大小：330K
- 年卷期：v.16,no.11(May 27, 1997)
- ISSN：1520-6041
文摘
Oxidation of the mixed-metal clusterCp*WRe2(CCR)(CO)9 (1, Cp* =C5Me5; R = Ph andC(Me)=CH2) with dioxygen in solution at 100 
deg.gif">C affordsthe oxo clustersCp*W(O)Re2(CCR)(CO)8, (2a, R = Ph; and 2b, R =C(Me)=CH2. Treatment of 2 with CO at 110deg.gif">C providesthe clustersCp*W(O)Re2(CCR)(CO)9(4), which revert back to 2 by removal of one COuponthermolysis. Both compounds 2 and 4 containan open triangular skeletal arrangement, amultisite bound acetylide ligand, and a terminal oxo ligand attached tothe W atom. Complex2a reacts with dihydrogen to form a mixture of three clustercomplexes: the acetylide clusterCp*WRe2(
-O)(-H)2(CCPh)(CO)6(5a), alkenyl clusterCp*W(O)Re2(CHCHPh)(CO)8(6a), andthe alkylidene clusterCp*W(O)Re2(-H)(CHCH2Ph)(CO)8(7a), which are formally producedby addition of two H2 and elimination of two CO molecules,transferring one H2 to theacetylide ligand and incorporation of one H2 molecule to6a, respectively. For thevinylacetylide compound 2b, it reacts with dihydrogen undersimilar conditions to furnisha mixture of the above mentioned clusters 5b, 6b,and 7b, together with a fourth allenylclusterCp*WRe2(-O)(CHCCMe2)(CO)7(8), which is probably produced through a 1,3-H-migration on the alkenyl ligand CH=CHC(Me)=CH2 in6b. The X-ray structural analysisof these oxo cluster compounds, their spectroscopic data, and themechanistic studies of theconversion from acetylide clusters 2, 4, and5 to alkenyl clusters 6, alkylidene clusters7,and allenyl cluster 8 are presented.
deg.gif">C affordsthe oxo clustersCp*W(O)Re2(CCR)(CO)8, (2a, R = Ph; and 2b, R =C(Me)=CH2. Treatment of 2 with CO at 110deg.gif">C providesthe clustersCp*W(O)Re2(CCR)(CO)9(4), which revert back to 2 by removal of one COuponthermolysis. Both compounds 2 and 4 containan open triangular skeletal arrangement, amultisite bound acetylide ligand, and a terminal oxo ligand attached tothe W atom. Complex2a reacts with dihydrogen to form a mixture of three clustercomplexes: the acetylide clusterCp*WRe2(-O)(-H)2(CCPh)(CO)6(5a), alkenyl clusterCp*W(O)Re2(CHCHPh)(CO)8(6a), andthe alkylidene clusterCp*W(O)Re2(-H)(CHCH2Ph)(CO)8(7a), which are formally producedby addition of two H2 and elimination of two CO molecules,transferring one H2 to theacetylide ligand and incorporation of one H2 molecule to6a, respectively. For thevinylacetylide compound 2b, it reacts with dihydrogen undersimilar conditions to furnisha mixture of the above mentioned clusters 5b, 6b,and 7b, together with a fourth allenylclusterCp*WRe2(-O)(CHCCMe2)(CO)7(8), which is probably produced through a 1,3-H-migration on the alkenyl ligand CH=CHC(Me)=CH2 in6b. The X-ray structural analysisof these oxo cluster compounds, their spectroscopic data, and themechanistic studies of theconversion from acetylide clusters 2, 4, and5 to alkenyl clusters 6, alkylidene clusters7,and allenyl cluster 8 are presented.