Diphosphine substitution in pentakis(arylisocyanide)cobalt(I) complexes; 31P NMR, cyclic voltammetric and ESI mass spectrometry studies

F. Foster Mbaiwa, C. A.L. Becker

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Five new complexes of the type [Co(CNC6H3iPr 2-2,6)4PPh2-R′-PPh2]X, X = BF4, ClO4; R′ =-(CH2)2- (1), -(CH2)3- (2), -CHCH-trans (3), -CC- (4) and -C 6H4-p (5); and two new bimetallic complexes, [{Co(CNC 6H3iPr2-2,6)4}2(μ- PPh2(CH2)3PPh2)](ClO 4)2 (6) and [{Co(CNC6H3iPr 2-2,6)4}2(μ-PPh2C 6H4PPh2-p)](ClO4)2 (7), have been synthesized and characterized by various spectroscopic methods.Known monometallic and bimetallic complexes bearing the ligand CNC6H 3Et2-2,6 instead of CNC6H3iPr 2-2,6 have been included in the 31P NMR, cyclic voltammetric and mass spectrometry studies.Comparison of the CNC 6H3iPr2-2,6 with the CNC6H 3Et2-2,6 complexes shows that the increased steric bulkiness of the former makes it more suitable for synthesis of the monometallic complexes, whilst the CNC6H3Et2-2,6 is more apt to give bimetallic complexes.Thus, the two arylisocyanides are complementary with respect to synthesis of the monometallic and bimetallic complexes.The 31P NMR indicates that the diphosphines in monometallic complexes behave as non-fluxional, monodentate ligands at ambient temperature, with 31P-31P coupling shown for the PPh2CH 2PPh2, PPh2(CH2)2PPh 2 and PPh2CCPPh2 ligands. Cyclic voltammetry fails to show electronic communication in the bimetallic complexes, and mass spectrometry indicates significantly greater stability for fragments containing potentially chelating diphosphines as compared to diphosphines that cannot chelate.

Original languageEnglish
Pages (from-to)1041-1049
Number of pages9
JournalInorganica Chimica Acta
Volume359
Issue number4
DOIs
Publication statusPublished - Mar 1 2006

Fingerprint

Cobalt
Mass spectrometry
Substitution reactions
cobalt
mass spectroscopy
Ligands
Nuclear magnetic resonance
substitutes
nuclear magnetic resonance
ligands
Bearings (structural)
synthesis
Chelation
chelates
Cyclic voltammetry
ambient temperature
communication
fragments
Communication
electronics

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

@article{76a87d7082fd46528fb98471d2b38951,
title = "Diphosphine substitution in pentakis(arylisocyanide)cobalt(I) complexes; 31P NMR, cyclic voltammetric and ESI mass spectrometry studies",
abstract = "Five new complexes of the type [Co(CNC6H3iPr 2-2,6)4PPh2-R′-PPh2]X, X = BF4, ClO4; R′ =-(CH2)2- (1), -(CH2)3- (2), -CHCH-trans (3), -CC- (4) and -C 6H4-p (5); and two new bimetallic complexes, [{Co(CNC 6H3iPr2-2,6)4}2(μ- PPh2(CH2)3PPh2)](ClO 4)2 (6) and [{Co(CNC6H3iPr 2-2,6)4}2(μ-PPh2C 6H4PPh2-p)](ClO4)2 (7), have been synthesized and characterized by various spectroscopic methods.Known monometallic and bimetallic complexes bearing the ligand CNC6H 3Et2-2,6 instead of CNC6H3iPr 2-2,6 have been included in the 31P NMR, cyclic voltammetric and mass spectrometry studies.Comparison of the CNC 6H3iPr2-2,6 with the CNC6H 3Et2-2,6 complexes shows that the increased steric bulkiness of the former makes it more suitable for synthesis of the monometallic complexes, whilst the CNC6H3Et2-2,6 is more apt to give bimetallic complexes.Thus, the two arylisocyanides are complementary with respect to synthesis of the monometallic and bimetallic complexes.The 31P NMR indicates that the diphosphines in monometallic complexes behave as non-fluxional, monodentate ligands at ambient temperature, with 31P-31P coupling shown for the PPh2CH 2PPh2, PPh2(CH2)2PPh 2 and PPh2CCPPh2 ligands. Cyclic voltammetry fails to show electronic communication in the bimetallic complexes, and mass spectrometry indicates significantly greater stability for fragments containing potentially chelating diphosphines as compared to diphosphines that cannot chelate.",
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Diphosphine substitution in pentakis(arylisocyanide)cobalt(I) complexes; 31P NMR, cyclic voltammetric and ESI mass spectrometry studies. / Mbaiwa, F. Foster; Becker, C. A.L.

In: Inorganica Chimica Acta, Vol. 359, No. 4, 01.03.2006, p. 1041-1049.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Diphosphine substitution in pentakis(arylisocyanide)cobalt(I) complexes; 31P NMR, cyclic voltammetric and ESI mass spectrometry studies

AU - Mbaiwa, F. Foster

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N2 - Five new complexes of the type [Co(CNC6H3iPr 2-2,6)4PPh2-R′-PPh2]X, X = BF4, ClO4; R′ =-(CH2)2- (1), -(CH2)3- (2), -CHCH-trans (3), -CC- (4) and -C 6H4-p (5); and two new bimetallic complexes, [{Co(CNC 6H3iPr2-2,6)4}2(μ- PPh2(CH2)3PPh2)](ClO 4)2 (6) and [{Co(CNC6H3iPr 2-2,6)4}2(μ-PPh2C 6H4PPh2-p)](ClO4)2 (7), have been synthesized and characterized by various spectroscopic methods.Known monometallic and bimetallic complexes bearing the ligand CNC6H 3Et2-2,6 instead of CNC6H3iPr 2-2,6 have been included in the 31P NMR, cyclic voltammetric and mass spectrometry studies.Comparison of the CNC 6H3iPr2-2,6 with the CNC6H 3Et2-2,6 complexes shows that the increased steric bulkiness of the former makes it more suitable for synthesis of the monometallic complexes, whilst the CNC6H3Et2-2,6 is more apt to give bimetallic complexes.Thus, the two arylisocyanides are complementary with respect to synthesis of the monometallic and bimetallic complexes.The 31P NMR indicates that the diphosphines in monometallic complexes behave as non-fluxional, monodentate ligands at ambient temperature, with 31P-31P coupling shown for the PPh2CH 2PPh2, PPh2(CH2)2PPh 2 and PPh2CCPPh2 ligands. Cyclic voltammetry fails to show electronic communication in the bimetallic complexes, and mass spectrometry indicates significantly greater stability for fragments containing potentially chelating diphosphines as compared to diphosphines that cannot chelate.

AB - Five new complexes of the type [Co(CNC6H3iPr 2-2,6)4PPh2-R′-PPh2]X, X = BF4, ClO4; R′ =-(CH2)2- (1), -(CH2)3- (2), -CHCH-trans (3), -CC- (4) and -C 6H4-p (5); and two new bimetallic complexes, [{Co(CNC 6H3iPr2-2,6)4}2(μ- PPh2(CH2)3PPh2)](ClO 4)2 (6) and [{Co(CNC6H3iPr 2-2,6)4}2(μ-PPh2C 6H4PPh2-p)](ClO4)2 (7), have been synthesized and characterized by various spectroscopic methods.Known monometallic and bimetallic complexes bearing the ligand CNC6H 3Et2-2,6 instead of CNC6H3iPr 2-2,6 have been included in the 31P NMR, cyclic voltammetric and mass spectrometry studies.Comparison of the CNC 6H3iPr2-2,6 with the CNC6H 3Et2-2,6 complexes shows that the increased steric bulkiness of the former makes it more suitable for synthesis of the monometallic complexes, whilst the CNC6H3Et2-2,6 is more apt to give bimetallic complexes.Thus, the two arylisocyanides are complementary with respect to synthesis of the monometallic and bimetallic complexes.The 31P NMR indicates that the diphosphines in monometallic complexes behave as non-fluxional, monodentate ligands at ambient temperature, with 31P-31P coupling shown for the PPh2CH 2PPh2, PPh2(CH2)2PPh 2 and PPh2CCPPh2 ligands. Cyclic voltammetry fails to show electronic communication in the bimetallic complexes, and mass spectrometry indicates significantly greater stability for fragments containing potentially chelating diphosphines as compared to diphosphines that cannot chelate.

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