Weakening of Carbide–Platinum Bonds as a Probe for Ligand Donor Strengths

TY - JOUR

T1 - Weakening of Carbide–Platinum Bonds as a Probe for Ligand Donor Strengths

AU - Reinholdt, Anders

AU - Bendix, Jesper

PY - 2017/10/16

Y1 - 2017/10/16

N2 - We report the observation of the weakening of the RuC-Pt single bond in (Cy3P)2Cl2Ru≡C-PtCl2-L (Ru≡C-Pt-L) complexes, leading to the incipient formation of the terminal ruthenium carbide complex, (Cy3P)2Cl2Ru≡C (RuC). In the solid state, elongation of RuC-Pt bonds illustrates the degree of weakening, and in solution, decreasing platinum-carbide coupling constants and increasing carbide chemical shifts reveal weaker interaction through the carbide bridge, as the electron donating ability of L becomes progressively stronger. For the bridging carbide ligands, the chemical shifts and coupling constants to platinum are linearly dependent, and NMR data for parent RuC conform to this relationship, providing a spectroscopic means of determining the strength of the RuC-Pt linkages relative to dissociated RuC. The pliancy of the Ru≡C-Pt-L fragment with regard to the identity of L establishes the carbide-bridged complexes as remarkably wide-ranging and sensitive probes for ligand donor abilities.

AB - We report the observation of the weakening of the RuC-Pt single bond in (Cy3P)2Cl2Ru≡C-PtCl2-L (Ru≡C-Pt-L) complexes, leading to the incipient formation of the terminal ruthenium carbide complex, (Cy3P)2Cl2Ru≡C (RuC). In the solid state, elongation of RuC-Pt bonds illustrates the degree of weakening, and in solution, decreasing platinum-carbide coupling constants and increasing carbide chemical shifts reveal weaker interaction through the carbide bridge, as the electron donating ability of L becomes progressively stronger. For the bridging carbide ligands, the chemical shifts and coupling constants to platinum are linearly dependent, and NMR data for parent RuC conform to this relationship, providing a spectroscopic means of determining the strength of the RuC-Pt linkages relative to dissociated RuC. The pliancy of the Ru≡C-Pt-L fragment with regard to the identity of L establishes the carbide-bridged complexes as remarkably wide-ranging and sensitive probes for ligand donor abilities.

U2 - 10.1021/acs.inorgchem.7b01956

DO - 10.1021/acs.inorgchem.7b01956

M3 - Journal article

C2 - 28945348

SN - 0020-1669

VL - 56

SP - 12492

EP - 12497

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -