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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Paper

J. Chem. Soc., Dalton Trans., 1980, 511 - 518, DOI: 10.1039/DT9800000511

Synthesis of trimethylphosphine complexes of rhodium and ruthenium. X-Ray crystal structures of tetrakis(trimethylphosphine)rhodium(I) chloride and chlorotris(trimethylphosphine)rhodium(I)

Richard A. Jones, Fernando Mayor Real, Geoffrey Wilkinson, Anita M. R. Galas, Michael B. Hursthouse and K. M. Abdul Malik

The synthesis and characterization of the following trimethylphosphine complexes of rhodium and ruthenium are reported; [Rh(PMe3)4]Cl, (A), RhCl(PMe3)3, (B), [Rh(PMe3)3]X, (X = PF6, BPh4), [RhH2(PMe3)4]Cl, RhCl(CO)(PMe3)2, [Rh(PMe3)3(CH2Cl2)]Cl, [RuCl(PMe3)2]2, [RuCl(PMe3)4]BF4, trans-RuCl2(PMe3)4, [RuCl(PMe3)4]2Cl2 and RuHCl(PMe3)4.The crystal structures of (A) and (B) have been determined by single-crystal X-ray diffraction. Compound (A) is orthorhombic, space group Ccmm with a= 12.366, b= 13.584, c= 12.554 Å, and Z= 4; (B) is triclinic, space group P1 with a= 8.842, b= 8.982, c= 11.825 Å, = 98.74, = 92.38, = 116.09°, Z= 2. The structures were determined using 1 476 and 2 695 observed intesities measured on an automatic diffractometer and refined to R values of 0.030 and 0.023 for (A) and (B) respectively. The geometries of both the RhP4+ cation and RhP3Cl molecule can be described as square planar, with considerable tetrahedral distortion as a result of steric crowding. Rh–P distances in (A) are 2.295 and 2.299(1)Å, whilst in (B) Rh–P bonds trans to each other are 2.295 and 2.296(1)Å, but trans to Cl 2.203 Å; Rh–Cl is 2.410 Å.