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	Synthesis of Coordinated eta(2)-alpha,beta-Unsaturated Ketone Osmacycles from an Osmium-Coordinated Alkyne Alcohol Complex
	Gong, Lei ; Lin, Yumei ; Wen, Ting Bin ; Wen TB(温庭斌) ; Xia, Haiping ; Xia HP(夏海平)
	2009-01
英文摘要	The study on the reactivity of an osmium-coordinated alkyne alcohol complex OsCl2(CH=C(PPh3)CH(OH)-eta(2)-C CH)(PPh3)(2) (1) has been carried out. Treatment of 1 with acetic acid, ethylene diamine, 2,2'-bipyridine, trimethylphospine, or tributylphosphine led to the formation of several coordinated eta(2)-alpha,beta-unsaturated ketone osmacycles, including OsCl2(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PPh3)(2) (3), [OsCl(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PPh3)(H2NCH2CH2NH2)]Cl (4), [OsCl(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PPh3)(2,2'-bipy)]Cl (5), OsCl2(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PMe3)(2) (6), [OsCl(CH=C(PPh3)C(O)-eta(2)-CH=CH2(PMe3)(3)]Cl (8), and OsCl2(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PBu3)(2) (9). Similar chemistry was also observed starting from OsBr2(CH=C(PPh3)CH(OH)-eta(2)-C CH)(PPh3)(2) (10), which afforded OsBr2(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PPh3)(2) (11) on treatment with acetic acid. All these cyclic alpha,beta-unsaturated ketone complexes are air-stable in the solid state, and most of them are also stable in solution except for OsCl2(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PMe3)(2) (6) and [OsCl(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(PMe3)(3)]Cl (8). Complex 8 can isomerize to the osmaphenol [OsCl(CHC(PPh3)C(OH)-CHCH)(PMe3)(3)]Cl (12) as the major product in dry chloroform, but transforms into the osmafuran [Os(CO)(CHC(PPh3)C(CH3)O)(PMe3)(3)]Cl-2 (13) in wet chloroform, while complex 6 is stable in dry solvent, but can convert to the osmafuran [OsCl(CO)(CHC(PPh3)C(CH3)O)(PMe3)(2)]Cl (14). The remarkable thermostability and chemical stability of the coordinated alpha,beta-unsaturated ketone osmacycles have been studied preliminarily with 3 as a representative example. The coordinated alpha,beta-unsaturated ketone metallacyclic framework of 3 is stable in different ligand environments. For example, treatment of 3 with carbon monoxide led only to ligand substitution to produce OsCl2(CH=C(PPh3)C(O)-eta(2)-CH=CH2)(CO)(PPh3) (15).; National Science Foundation of China ; Young Talent Project of Fujian Provincial Department of Science Technology [2007173095]; Program for New Century Excellent Talents in Fujian Province University ; [20572089]; [20772100]
语种	英语
出版者	AMER CHEMICAL SOC
内容类型	期刊论文
源URL	[http://dx.doi.org/doi:10.1021/om800907v]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Gong, Lei,Lin, Yumei,Wen, Ting Bin,et al. Synthesis of Coordinated eta(2)-alpha,beta-Unsaturated Ketone Osmacycles from an Osmium-Coordinated Alkyne Alcohol Complex[J],2009.
APA	Gong, Lei,Lin, Yumei,Wen, Ting Bin,温庭斌,Xia, Haiping,&夏海平.(2009).Synthesis of Coordinated eta(2)-alpha,beta-Unsaturated Ketone Osmacycles from an Osmium-Coordinated Alkyne Alcohol Complex..
MLA	Gong, Lei,et al."Synthesis of Coordinated eta(2)-alpha,beta-Unsaturated Ketone Osmacycles from an Osmium-Coordinated Alkyne Alcohol Complex".(2009).

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