Oxidative additions of dichloromethane and cyclo-octasulfur to rhodium(I) complexes containing (2-aminoethyl)-dimethylphosphine or -diphenylphosphine
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Kazuo Kashiwabara, Akira Morikawa, Takayoshi Suzuki, Kiyoshi Isobe and Kazuyuki Tatsumi
Abstract
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![[hair space]](https://www.rsc.org/images/entities/char_200a.gif)
′)-[Rh(O2
)(edmp)2]+5 is also described.
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