Homo- and heteronuclear complexes based on arene ruthenium complexes bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp)

Quasi-octahedral complexes of pentamethylcyclopentadienyliridium(iii) bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp)

“…A similar trend has been noted in the rhodium and ruthenium analogs. 4,5 The detailed structure was confirmed by an X-ray analysis of anti-4 (Fig. 2).…”

“…In the rhodium analogs, similar reactions recovered the starting materials, 4 whereas in the ruthenium complexes the reactions cleave a Ru-P 3 coordination bond, giving (C 6 Me 6 )RuCl 2 (XylNC) and [(C 6 Me 6 )RuCl(dpmp-P 1 ,P 2 )](PF 6 ) accompanied by no change of geometry. 5 Thus, the temporary metal-P bond cleavage in a four-membered ring occurred in the syn-iridium complex, and no cleavage proceeded for the rhodium and ruthenium complexes. The four-membered rings for the Rh and Ru complexes are superior in stability to that for the Ir complex.…”

“…from those for the rhodium and ruthenium analogs. 4,5 Mononuclear complexes anti-and syn-[Cp*IrCl(dpmp-P 1 ,P 2 )](PF 6 ) ( 4) could be prepared by treatment of Cp*IrCl 2 (MDMPP-P) (3a), Cp*IrCl 2 (BDMPP-P) (3b) or Cp*IrCl 2 (TDMPP-P) (3c) with dpmp in the presence of KPF 6 or the substitution reaction of [Cp*IrCl(BDMPP-P,OMe)](PF 6 ) with dpmp (Scheme 1). Based on the 1 H NMR spectra of the reaction mixtures, the ratio of anti-4 and syn-4 is ca.…”

“…The latter angles are comparable with those found in the Rh or ruthenium complexes bearing a similar anti-structure. 4,5 Crystal structure of anti-4. A perspective drawing of anti-4 with the atomic numbering scheme is given in Fig.…”

“…Previously we have reported that the reactions of [Cp*RhCl 2 ] 2 (Cp* = C 5 Me 5 ) or [(arene)RuCl 2 ] 2 (arene = p-cymene, C 6 Me 6 ) with dpmp in the presence of KPF 6 generated mono-and binuclear complexes containing four-membered rings deriving from coordination of a terminal P atom and a central P atom of the dpmp ligand to the metal atoms. [3][4][5] These complexes consist of two diastereomers, anti-form and syn-form, 6 because of the presence of two chiral centers at the metal atom and a central P atom of the dpmp ligand.…”