Journal of the Chemical Society, Dalton Transactions p. 2275 - 2283 (1996)
Update date:2022-07-29
Topics:
Martin, Marta
Gevert, Olaf
Werner, Helmut
An efficient method for the preparation of the chelate complex [RuCl2(κ2P,O-Pri2PCH 2CH2OMe)2] 2, using [{RuCl2(C8H12)}n] 1 as starting material, has been developed. Compound 2 reacts with terminal alkynes HC≡CR (R = Ph, C6H4Me-p or C6H4C≡CH-m) in the presence of Ag(O3SCF3) to give the octahedral cationic vinylidene complexes [RuCl(=C=CHR)(κ2P,O-Pri2PCH 2CH2OMe)2][O3SCF3] 4-6 in 70-80% yield. The parent derivative 3 (R = H) has been prepared analogously but is stable only under an acetylene atmosphere. Crystal structural analysis of 4 (R = Ph) confirms a cis arrangement of the chloro and vinylidene ligands. Treatment of 4 with basic Al2O3 produces, by deprotonation, a mixture of two isomers [RuCl(C≡CPh)(κ2P,O-Pri2PCH 2CH2OMe)2] 7, 8 with the alkynyl and chloro ligands in either cis or trans disposition. Compounds 7, 8 easily react by partial cleavage of the chelate bonds to give the corresponding dicarbonyl derivatives [RuCl(C≡CPh)(CO)2(κP-Pri2PCH 2CH2OMe)2] 9, 10. The isomeric mixture can be completely converted into the thermodynamically preferred species 9 with the two CO and the alkynyl and chloro ligands cis disposed. The neutral vinylidene complexes [RuX2(=C=CHPh)(κP-Pri2PCH 2CH2OMe)(κ2P,O-Pri 2PCH2CH2OMe)] (X = CN, I or Br) were obtained from 4 and KCN, NaI and LiBr, respectively. The reaction of 2 with propargylic alcohols HC≡CCR(Ph)OH in the presence of Ag(O3SCF3), followed by treatment with acidic Al2O3, afforded the cationic allenylidene compounds [RuCl{=C=C=C(Ph)R}(κ2P,O-Pri2PCH 2CH2OMe)2]-[O3SCF3] (R = Ph or C6H4Me-O) in moderate yields. The crystal structure where R = Ph has been determined and reveals an almost linear Ru=C=C=C chain with one of the methoxy groups trans to the allenylidene ligand. While the R = C6H4Me-o derivative reacts with CO to give the cationic carbonyl compound [RuCl(CO)(κ2P,O-Pri2PCH 2CH2OMe)2][O3SCF3], the reaction of 4 with CO gives a mixture of this complex, 9/10, and trans,trans,trans-[RuCl2(CO)2(κP-Pri 2PCH2CH2OMe)2]. The latter is formed quantitatively from 2 and carbon monoxide.
Jinan Kaypharm Chemical Co.,Ltd
Contact:86-0531-86986780
Address:Room101,No189-2,Huayuan Road,Jinan City,Shandong Province
Sichuan Highlight Fine Chemicals Co., Ltd.
Contact:+86-28-8525 1605
Address:A5-102 Airport base,388 West Airport Huang He Zhong Lu,2 Section
Tianjin Anda North Industrial & Business Co.Ltd.
Contact:86-22-24999306
Address:No.11 Erwei Road,Dongli Development Area,Tianjin,China
taizhou creating bio-pharm co.,ltd.
Contact:+86- 576- 88827176
Address:715 room ,unit A.junyue Building,Jiaojiang,Taizhou,Zhejiang,China
Hangzhou JINLAN Pharm-Drugs Technology Co., Ltd
website:http://www.jlpharms.com
Contact:86-571-86982636
Address:Rm A606, Fuyi Center, jianqiao street
Doi:10.1080/00397919808004886
(1998)Doi:10.1039/c3pp50186h
(2013)Doi:10.1016/j.tetlet.2005.12.083
(2006)Doi:10.1021/om960072s
(1996)Doi:10.1016/0022-1139(96)03431-8
(1996)Doi:10.1002/hlca.19960790304
(1996)
