Oxidative additions of dichloromethane and cyclo-octasulfur to rhodium(I) complexes containing (2-aminoethyl)-dimethylphosphine or -diphenylphosphine

Kazuo Kashiwabara, Akira Morikawa, Takayoshi Suzuki, Kiyoshi Isobe, Kazuyuki Tatsumi

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The oxidative-addition reactions of dichloromethane and cyclo-octasulfur with rhodium(I) complexes containing (2-aminoethyl)dimethylphosphine (edmp) or (2-aminoethyl)diphenylphosphine (edpp) have been examined. The reactions of [{RhCl(cod)}2] (cod = cycloocta-1,5-diene) with edmp and with edpp in dichloromethane yield cationic adducts trans(Cl,C)cis(P,P′)-[RhCl(CH2Cl)(edmp)2] + 1 and trans(Cl,C)cis(P,P′)-[RhCl(CH2Cl)(edpp)2] + 2, respectively. X-Ray analyses of these complexes revealed that the Rh-Cl bond lengths are considerably elongated compared with those of the corresponding dichloro complexes trans(Cl,Cl′)cis(P,P′)-[RhCl2(edmp)2] + and trans(Cl,Cl′)cis(P,P′)-[RhCl2(edpp)2] + due to the strong trans influence of the chloromethyl donor group. The Rh-C bonds in complexes 1, 2 and trans-[RhCl(CH2Cl)(dmpe)2]+ are 2.050(7) < 2.078(7) < 2.162(2) Å, respectively. This order reflects the differences in the steric bulk around rhodium(III) centre as well as the strength of the trans influence toward the trans-positioned Rh-Cl bond. Complex 2 reacted further with S8 to give a mixture of trans(P,N)-[Rh(S4)(edpp)2]+ 3a and trans(P,N)-[Rh(S5)(edpp)2]+ 3b, however such a reaction does not occur for 1. On the other hand, direct addition of S8 to [Rh(edmp)2]+ in methanol resulted in the formation of trans(N,N′)-[Rh(S4)(edmp)2]+ 4a and a small amount of the S5 complex 4b. The analogous reaction with [Rh(edpp)2]+ gave a mixture of 3a and 3b. X-Ray analyses revealed that 3a and 3b are cocrystallized in the ratio of 1:1. The preparation of trans(N,N′)-[Rh(O2)(edmp)2]+ 5 is also described.

Original languageEnglish
Pages (from-to)1075-1081
Number of pages7
JournalJournal of the Chemical Society - Dalton Transactions
Issue number6
Publication statusPublished - Mar 21 1997
Externally publishedYes

ASJC Scopus subject areas

  • General Chemistry


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