Novel mixed-metal-alkynyl complexes stabilised by di-imine ligands: Synthesis, characterisation and electrochemistry of [(tBu2bipy)Pt(C≡CR)2M(SCN)] (R = C6H4Me, SiMe3; M = Cu, Ag)

Christopher J. Adams; Paul R. Raithby

doi:10.1016/S0022-328X(98)01120-6

Novel mixed-metal-alkynyl complexes stabilised by di-imine ligands: Synthesis, characterisation and electrochemistry of [(^tBu₂bipy)Pt(C≡CR)₂M(SCN)] (R = C₆H₄Me, SiMe₃; M = Cu, Ag)

Christopher J. Adams, Paul R. Raithby

University of Cambridge

Research output: Contribution to journal › Article › peer-review

45 Citations (SciVal)

Abstract

Reaction of (4,4′-bis-tert-butyl-2,2′-dipyridyl) platinum bis-alkynyl [(^tBu₂bipy)Pt(C≡CR)₂] (R = C₆H₄Me 1a, SiMe₃ 1b) with Group 11 metal thiocyanate salts (M = Cu, Ag) affords 1:1 mixed-metal complexes [(^tBu₂bipy)Pt(C≡CR)₂M(SCN)] (M = Cu, R = C₆H₄Me 2a, SiMe₃ 2b; M = Ag, R = C₆H₄Me 3a, SiMe₃ 3b). X-ray analyses of the complexes 2a and 3b show that the group 11 metal is bonded in an η² fashion to two carbon-carbon triple bonds so that the co-ordination geometry is trigonal planar. The Pt atom geometry in both complexes is square planar. An electrochemical study of the copper complexes 2a and 2b reveals one fully reversible one electron reduction that is consistent with the first reduction of the co-ordinated bipyridyl ligand. There is also an irreversible one electron oxidation that corresponds to the Cu^I to Cu^II transition.

Original language	English
Pages (from-to)	178-185
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	578
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(98)01120-6
Publication status	Published - 22 Apr 1999

Funding

The authors are grateful to the E.P.S.R.C. for financial support (to C.J. Adams). The authors would also like to thank Johnson Matthey plc. for the generous loan of platinum salts.

Keywords

Alkyn5es
Bipyridyl
Copper
Crystal structures
Platinum
Silver

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0022-328X(98)01120-6

Cite this

Novel mixed-metal-alkynyl complexes stabilised by di-imine ligands: Synthesis, characterisation and electrochemistry of [(^tBu₂bipy)Pt(C≡CR)₂M(SCN)] (R = C₆H₄Me, SiMe₃; M = Cu, Ag). / Adams, Christopher J.; Raithby, Paul R.
In: Journal of Organometallic Chemistry, Vol. 578, No. 1-2, 22.04.1999, p. 178-185.

Research output: Contribution to journal › Article › peer-review

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abstract = "Reaction of (4,4′-bis-tert-butyl-2,2′-dipyridyl) platinum bis-alkynyl [(tBu2bipy)Pt(C≡CR)2] (R = C6H4Me 1a, SiMe3 1b) with Group 11 metal thiocyanate salts (M = Cu, Ag) affords 1:1 mixed-metal complexes [(tBu2bipy)Pt(C≡CR)2M(SCN)] (M = Cu, R = C6H4Me 2a, SiMe3 2b; M = Ag, R = C6H4Me 3a, SiMe3 3b). X-ray analyses of the complexes 2a and 3b show that the group 11 metal is bonded in an η2 fashion to two carbon-carbon triple bonds so that the co-ordination geometry is trigonal planar. The Pt atom geometry in both complexes is square planar. An electrochemical study of the copper complexes 2a and 2b reveals one fully reversible one electron reduction that is consistent with the first reduction of the co-ordinated bipyridyl ligand. There is also an irreversible one electron oxidation that corresponds to the CuI to CuII transition.",

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N2 - Reaction of (4,4′-bis-tert-butyl-2,2′-dipyridyl) platinum bis-alkynyl [(tBu2bipy)Pt(C≡CR)2] (R = C6H4Me 1a, SiMe3 1b) with Group 11 metal thiocyanate salts (M = Cu, Ag) affords 1:1 mixed-metal complexes [(tBu2bipy)Pt(C≡CR)2M(SCN)] (M = Cu, R = C6H4Me 2a, SiMe3 2b; M = Ag, R = C6H4Me 3a, SiMe3 3b). X-ray analyses of the complexes 2a and 3b show that the group 11 metal is bonded in an η2 fashion to two carbon-carbon triple bonds so that the co-ordination geometry is trigonal planar. The Pt atom geometry in both complexes is square planar. An electrochemical study of the copper complexes 2a and 2b reveals one fully reversible one electron reduction that is consistent with the first reduction of the co-ordinated bipyridyl ligand. There is also an irreversible one electron oxidation that corresponds to the CuI to CuII transition.

AB - Reaction of (4,4′-bis-tert-butyl-2,2′-dipyridyl) platinum bis-alkynyl [(tBu2bipy)Pt(C≡CR)2] (R = C6H4Me 1a, SiMe3 1b) with Group 11 metal thiocyanate salts (M = Cu, Ag) affords 1:1 mixed-metal complexes [(tBu2bipy)Pt(C≡CR)2M(SCN)] (M = Cu, R = C6H4Me 2a, SiMe3 2b; M = Ag, R = C6H4Me 3a, SiMe3 3b). X-ray analyses of the complexes 2a and 3b show that the group 11 metal is bonded in an η2 fashion to two carbon-carbon triple bonds so that the co-ordination geometry is trigonal planar. The Pt atom geometry in both complexes is square planar. An electrochemical study of the copper complexes 2a and 2b reveals one fully reversible one electron reduction that is consistent with the first reduction of the co-ordinated bipyridyl ligand. There is also an irreversible one electron oxidation that corresponds to the CuI to CuII transition.

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