Journal of Organometallic Chemistry p. 288 - 297 (2000)
Update date:2022-08-03
Topics:
Abd-Elzaher, Mokhles M.
Froneck, Thomas
Roth, Gerhard
Gvozdev, Valentin
Fischer, Helmut
Photolysis of [M(CO)6] in CH2Cl2 gives [(CO)5M(CH2Cl2)] (M = Cr, W). Replacement of CH2Cl2 by arylacetylene, HC≡CC6H 4R-p (R = Me, H, Br), produces the thermolabile arylacetylene complexes [(CO)5M(HC≡CC6H4R-p)]. Addition of N-phenyl benzylideneimines, PhN = C(C6H4 R′-p)H (R′ = Me, H, Cl), to solutions of these alkyne complexes affords alkenyl(amino)carbene complexes, [(CO)5M=C(NPhH)C (C6H4R-p))=C(C6H4R′-p))H], and 2-azetidin-1-ylidene complexes, [(CO)5M=C-NPh-C(C 6H4R′-p)H-C(C6H4R-p)H]. The formation of the alkenyl(amino)carbene complexes is favored. The ratio alkenyl(amino)carbene/2-azetidin-l-ylidene complex is 2.5-3 for M = W and 6.5-8 for M = Cr. Both types of complexes are obtained as mixtures of isomers. The 2-azetidin-1-ylidene complexes are very likely formed by cycloaddition of the imines to the C=C bond of vinylidene complexes resulting from tautomerization of the alkyne complexes. The cycloaddition is highly stereoselective. Predominantly, the syn isomer is obtained (syn/anti ≥ 9). In contrast, the alkenyl(amino)carbene complexes are presumably derived from the alkyne complexes via cycloaddition of the imines to the coordinated alkyne and subsequent 1,2-hydrogen shift and ring opening. Preferentially, the E isomers (where both aryl substituents are cis with respect to the C=C bond) are produced. The structure of the major isomer of the alkenyl(amino)carbene complex [(CO)5W=C(NPhH)C(C6 H4Me-p)=C(Ph)H] has been established by X-ray structural analysis.
View MoreShaanxi HuaTai Bio-fine chemical company Ltd
Contact:86-029-87862197
Address:No. 5, 3rd Floor, 29 Yanta North Road, Beilin Dist.
Shandong Jiulong Hisince Pharmaceutical Co.,Ltd.
Contact:+86-15853188990
Address:Huadian Pioneer Park, Huadian Township, Qihe County, Dezhou City, Shandong, P.R.China
Fuxin Jintelai Fluorin Chemical Co., Ltd.
Contact:+86-0418-8229599
Address:, 7th Huagong Road, Fluorine industry development zone (Yimatu Town,Fumeng County),Fuxin City, Liaoning Province, China
Hangzhou Yanshan Chemical Co.,Ltd.
Contact:86-571- 87698076
Address:Room 1001, #1 Building, Zhongtian MCC, No.2 Youzhinong, Wenyi West Road, Xihu District, Hangzhou, China
Hangzhou Maytime Bio-Tech Co.,Ltd.
website:http://www.maytime.com.cn
Contact:+86-571-88925295 88920965
Address:NO.2-1701 Ganghui Central Ningwei Street, Xiaoshan Hangzhou Zhejiang China
Doi:10.1039/j39700000712
(1970)Doi:10.1016/S0960-894X(01)00334-1
(2001)Doi:10.1039/a910179i
(2000)Doi:10.1021/jo070629l
(2007)Doi:10.1016/S0040-4039(00)00266-5
(2000)Doi:10.1248/cpb.48.740
(2000)