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

Anders Reinholdt; Jesper Bendix

doi:10.1021/acs.inorgchem.7b01956

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

Anders Reinholdt, Jesper Bendix

Department of Chemistry

20 Citations (Scopus)

Abstract

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.

Original language	English
Journal	Inorganic Chemistry
Volume	56
Issue number	20
Pages (from-to)	12492-12497
Number of pages	6
ISSN	0020-1669
DOIs	https://doi.org/10.1021/acs.inorgchem.7b01956
Publication status	Published - 16 Oct 2017

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title = "Weakening of Carbide–Platinum Bonds as a Probe for Ligand Donor Strengths",

abstract = "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.",

author = "Anders Reinholdt and Jesper Bendix",

year = "2017",

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day = "16",

doi = "10.1021/acs.inorgchem.7b01956",

language = "English",

volume = "56",

pages = "12492--12497",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

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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 -

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

Abstract

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