Synthesis, electrochemistry, and reactivity of half-sandwich ruthenium complexes bearing metallocene-based bisphosphines

Anthony P. Shaw, Jack R. Norton, Daniela Buccella, Lauren A. Sites, Shannon S. Kleinbach, Daniel A. Jarem, Katherine M. Bocage, Chip Nataro

Research output: Contribution to journalArticle

Abstract

The bimetallic complexes CpRu(P-P)X [Cp = n 5-C 5H 5; X = Cl, H; P-P = dppf (1,1′-bis(diphenylphosphino)ferrocene) , dppr (1,1′-bis(diphenylphosphino)ruthenocene), dppo (1,1′- bis(diphenylphosphino)-osmocene), dippf (1,1′-bis(diisopropylphosphino) ferrocene), dcpf (1,1′-bis(dicyclohexylphosphino)ferrocene)], Cp*Ru(P-P)X [Cp* = n 5-C 5Me 5; X = Cl, H; P-P = dppf, dippf, dppomf (1,1′-bis(diphenylphosphino) octamethylferrocene), dppc (1,1′-bis(diphenylphosphino)cobaltocene)], [Cp*Ru(P-P)X] + (X = H, CCPh; P-P = dppc +), and [Cp*Ru(P-P)L] 2+ (L = CH 3CN, t-BuCN; P-P = dppc -) have been synthesized. Most of the chloride and hydride complexes have been studied by cyclic voltammetry. The X-ray structures of [Cp*Ru(dppc)CH 3CN][PF6] 2 and [Cp*Ru(dppc)CCPh] [PF 6] have been determined. Protonation of [Cp*Ru(dppc)CCPh] + gives the vinylidene complex [Cp*Ru(dppc)CCHPh] 2+. The Co(III/II) potential of the dppc + ligand undergoes a cathodic shift upon coordination in [Cp*Ru-(dppc)H] + and an anodic shift upon coordination in [Cp*Ru(dppc)CH3CN] . The 1H NMR spectrum of Cp*Ru(dppc)H is consistent with its formulation as a Co(II)/Ru(II) complex. As gauged by their reactivity toward iminium cations, the hydride complexes are poor hydride donors; proton and electron transfer are dominant. CpRu(dippf)H and CpRu(dcpf)H deprotonate iminium cations with acidic a-hydrogens. Cp*Ru(dppc)H is oxidized by the N-(benzylidene)pyrrolidinium cation, giving [Cp*Ru-(dppc)H] - and the vicinal diamine 1,2-bis(N-pyrrolidino)-1,2-diphenylethane. Most of the hydride complexes give rraw-dihydride cations upon protonation; an exception is [Cp*Ru(dppc)H] +, which forms a dihydrogen complex [Cp*Ru(dppc)(H2)]2+ with surprising kinetic stability. This dihydrogen complex is more acidic and less thermodynamically stable than its dihydride isomer. The H 2 ligand in [Cp*Ru(dppc)-(H 2)] 2+ is readily replaced by nitriles; the reaction with t-BuCN occurs by a dissociative mechanism.

Original languageEnglish (US)
Pages (from-to)3804-3814
Number of pages11
JournalOrganometallics
Volume28
Issue number13
DOIs
StatePublished - Jul 13 2009

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Bearings (structural)
Ruthenium
Electrochemistry
electrochemistry
ruthenium
hydrides
reactivity
cations
dihydrides
Hydrides
synthesis
Cations
methylidyne
Protonation
ligands
shift
nitriles
vinylidene
diamines
electron transfer

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Synthesis, electrochemistry, and reactivity of half-sandwich ruthenium complexes bearing metallocene-based bisphosphines. / Shaw, Anthony P.; Norton, Jack R.; Buccella, Daniela; Sites, Lauren A.; Kleinbach, Shannon S.; Jarem, Daniel A.; Bocage, Katherine M.; Nataro, Chip.

In: Organometallics, Vol. 28, No. 13, 13.07.2009, p. 3804-3814.

Research output: Contribution to journalArticle

Shaw, AP, Norton, JR, Buccella, D, Sites, LA, Kleinbach, SS, Jarem, DA, Bocage, KM & Nataro, C 2009, 'Synthesis, electrochemistry, and reactivity of half-sandwich ruthenium complexes bearing metallocene-based bisphosphines', Organometallics, vol. 28, no. 13, pp. 3804-3814. https://doi.org/10.1021/om900062a
Shaw, Anthony P. ; Norton, Jack R. ; Buccella, Daniela ; Sites, Lauren A. ; Kleinbach, Shannon S. ; Jarem, Daniel A. ; Bocage, Katherine M. ; Nataro, Chip. / Synthesis, electrochemistry, and reactivity of half-sandwich ruthenium complexes bearing metallocene-based bisphosphines. In: Organometallics. 2009 ; Vol. 28, No. 13. pp. 3804-3814.
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title = "Synthesis, electrochemistry, and reactivity of half-sandwich ruthenium complexes bearing metallocene-based bisphosphines",
abstract = "The bimetallic complexes CpRu(P-P)X [Cp = n 5-C 5H 5; X = Cl, H; P-P = dppf (1,1′-bis(diphenylphosphino)ferrocene) , dppr (1,1′-bis(diphenylphosphino)ruthenocene), dppo (1,1′- bis(diphenylphosphino)-osmocene), dippf (1,1′-bis(diisopropylphosphino) ferrocene), dcpf (1,1′-bis(dicyclohexylphosphino)ferrocene)], Cp*Ru(P-P)X [Cp* = n 5-C 5Me 5; X = Cl, H; P-P = dppf, dippf, dppomf (1,1′-bis(diphenylphosphino) octamethylferrocene), dppc (1,1′-bis(diphenylphosphino)cobaltocene)], [Cp*Ru(P-P)X] + (X = H, CCPh; P-P = dppc +), and [Cp*Ru(P-P)L] 2+ (L = CH 3CN, t-BuCN; P-P = dppc -) have been synthesized. Most of the chloride and hydride complexes have been studied by cyclic voltammetry. The X-ray structures of [Cp*Ru(dppc)CH 3CN][PF6] 2 and [Cp*Ru(dppc)CCPh] [PF 6] have been determined. Protonation of [Cp*Ru(dppc)CCPh] + gives the vinylidene complex [Cp*Ru(dppc)CCHPh] 2+. The Co(III/II) potential of the dppc + ligand undergoes a cathodic shift upon coordination in [Cp*Ru-(dppc)H] + and an anodic shift upon coordination in [Cp*Ru(dppc)CH3CN] . The 1H NMR spectrum of Cp*Ru(dppc)H is consistent with its formulation as a Co(II)/Ru(II) complex. As gauged by their reactivity toward iminium cations, the hydride complexes are poor hydride donors; proton and electron transfer are dominant. CpRu(dippf)H and CpRu(dcpf)H deprotonate iminium cations with acidic a-hydrogens. Cp*Ru(dppc)H is oxidized by the N-(benzylidene)pyrrolidinium cation, giving [Cp*Ru-(dppc)H] - and the vicinal diamine 1,2-bis(N-pyrrolidino)-1,2-diphenylethane. Most of the hydride complexes give rraw-dihydride cations upon protonation; an exception is [Cp*Ru(dppc)H] +, which forms a dihydrogen complex [Cp*Ru(dppc)(H2)]2+ with surprising kinetic stability. This dihydrogen complex is more acidic and less thermodynamically stable than its dihydride isomer. The H 2 ligand in [Cp*Ru(dppc)-(H 2)] 2+ is readily replaced by nitriles; the reaction with t-BuCN occurs by a dissociative mechanism.",
author = "Shaw, {Anthony P.} and Norton, {Jack R.} and Daniela Buccella and Sites, {Lauren A.} and Kleinbach, {Shannon S.} and Jarem, {Daniel A.} and Bocage, {Katherine M.} and Chip Nataro",
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TY - JOUR

T1 - Synthesis, electrochemistry, and reactivity of half-sandwich ruthenium complexes bearing metallocene-based bisphosphines

AU - Shaw, Anthony P.

AU - Norton, Jack R.

AU - Buccella, Daniela

AU - Sites, Lauren A.

AU - Kleinbach, Shannon S.

AU - Jarem, Daniel A.

AU - Bocage, Katherine M.

AU - Nataro, Chip

PY - 2009/7/13

Y1 - 2009/7/13

N2 - The bimetallic complexes CpRu(P-P)X [Cp = n 5-C 5H 5; X = Cl, H; P-P = dppf (1,1′-bis(diphenylphosphino)ferrocene) , dppr (1,1′-bis(diphenylphosphino)ruthenocene), dppo (1,1′- bis(diphenylphosphino)-osmocene), dippf (1,1′-bis(diisopropylphosphino) ferrocene), dcpf (1,1′-bis(dicyclohexylphosphino)ferrocene)], Cp*Ru(P-P)X [Cp* = n 5-C 5Me 5; X = Cl, H; P-P = dppf, dippf, dppomf (1,1′-bis(diphenylphosphino) octamethylferrocene), dppc (1,1′-bis(diphenylphosphino)cobaltocene)], [Cp*Ru(P-P)X] + (X = H, CCPh; P-P = dppc +), and [Cp*Ru(P-P)L] 2+ (L = CH 3CN, t-BuCN; P-P = dppc -) have been synthesized. Most of the chloride and hydride complexes have been studied by cyclic voltammetry. The X-ray structures of [Cp*Ru(dppc)CH 3CN][PF6] 2 and [Cp*Ru(dppc)CCPh] [PF 6] have been determined. Protonation of [Cp*Ru(dppc)CCPh] + gives the vinylidene complex [Cp*Ru(dppc)CCHPh] 2+. The Co(III/II) potential of the dppc + ligand undergoes a cathodic shift upon coordination in [Cp*Ru-(dppc)H] + and an anodic shift upon coordination in [Cp*Ru(dppc)CH3CN] . The 1H NMR spectrum of Cp*Ru(dppc)H is consistent with its formulation as a Co(II)/Ru(II) complex. As gauged by their reactivity toward iminium cations, the hydride complexes are poor hydride donors; proton and electron transfer are dominant. CpRu(dippf)H and CpRu(dcpf)H deprotonate iminium cations with acidic a-hydrogens. Cp*Ru(dppc)H is oxidized by the N-(benzylidene)pyrrolidinium cation, giving [Cp*Ru-(dppc)H] - and the vicinal diamine 1,2-bis(N-pyrrolidino)-1,2-diphenylethane. Most of the hydride complexes give rraw-dihydride cations upon protonation; an exception is [Cp*Ru(dppc)H] +, which forms a dihydrogen complex [Cp*Ru(dppc)(H2)]2+ with surprising kinetic stability. This dihydrogen complex is more acidic and less thermodynamically stable than its dihydride isomer. The H 2 ligand in [Cp*Ru(dppc)-(H 2)] 2+ is readily replaced by nitriles; the reaction with t-BuCN occurs by a dissociative mechanism.

AB - The bimetallic complexes CpRu(P-P)X [Cp = n 5-C 5H 5; X = Cl, H; P-P = dppf (1,1′-bis(diphenylphosphino)ferrocene) , dppr (1,1′-bis(diphenylphosphino)ruthenocene), dppo (1,1′- bis(diphenylphosphino)-osmocene), dippf (1,1′-bis(diisopropylphosphino) ferrocene), dcpf (1,1′-bis(dicyclohexylphosphino)ferrocene)], Cp*Ru(P-P)X [Cp* = n 5-C 5Me 5; X = Cl, H; P-P = dppf, dippf, dppomf (1,1′-bis(diphenylphosphino) octamethylferrocene), dppc (1,1′-bis(diphenylphosphino)cobaltocene)], [Cp*Ru(P-P)X] + (X = H, CCPh; P-P = dppc +), and [Cp*Ru(P-P)L] 2+ (L = CH 3CN, t-BuCN; P-P = dppc -) have been synthesized. Most of the chloride and hydride complexes have been studied by cyclic voltammetry. The X-ray structures of [Cp*Ru(dppc)CH 3CN][PF6] 2 and [Cp*Ru(dppc)CCPh] [PF 6] have been determined. Protonation of [Cp*Ru(dppc)CCPh] + gives the vinylidene complex [Cp*Ru(dppc)CCHPh] 2+. The Co(III/II) potential of the dppc + ligand undergoes a cathodic shift upon coordination in [Cp*Ru-(dppc)H] + and an anodic shift upon coordination in [Cp*Ru(dppc)CH3CN] . The 1H NMR spectrum of Cp*Ru(dppc)H is consistent with its formulation as a Co(II)/Ru(II) complex. As gauged by their reactivity toward iminium cations, the hydride complexes are poor hydride donors; proton and electron transfer are dominant. CpRu(dippf)H and CpRu(dcpf)H deprotonate iminium cations with acidic a-hydrogens. Cp*Ru(dppc)H is oxidized by the N-(benzylidene)pyrrolidinium cation, giving [Cp*Ru-(dppc)H] - and the vicinal diamine 1,2-bis(N-pyrrolidino)-1,2-diphenylethane. Most of the hydride complexes give rraw-dihydride cations upon protonation; an exception is [Cp*Ru(dppc)H] +, which forms a dihydrogen complex [Cp*Ru(dppc)(H2)]2+ with surprising kinetic stability. This dihydrogen complex is more acidic and less thermodynamically stable than its dihydride isomer. The H 2 ligand in [Cp*Ru(dppc)-(H 2)] 2+ is readily replaced by nitriles; the reaction with t-BuCN occurs by a dissociative mechanism.

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