TY - JOUR
T1 - Reactivity of coordinatively unsaturated bis(N-heterocyclic carbene) Pt(II) complexes toward H2. Crystal structure of a 14-electron Pt(II) hydride complex
AU - Rivada-Wheelaghan, Orestes
AU - Roselló-Merino, Marta
AU - Ortuno Maqueda, Manuel A
AU - Vidossich, Pietro
AU - Gutiérrez-Puebla, Enrique
AU - Lledós, Agustí
AU - Conejero, Salvador
PY - 2014/4/21
Y1 - 2014/4/21
N2 - The reactivity toward H2 of coordinatively unsaturated Pt(II) complexes, stabilized by N-heterocyclic carbene (NHC) ligands, is herein analyzed. The cationic platinum complexes [Pt(NHC′)(NHC)]+ (where NHC′ stands for a cyclometalated NHC ligand) react very fast with H2 at room temperature, leading to hydrogenolysis of the Pt-CH 2 bond and concomitant formation of hydride derivatives [PtH(NHC)2]+ or hydrido-dihydrogen complexes [PtH(H 2)(NHC)2]+. The latter species release H 2 when these compounds are subjected to vacuum. The X-ray structure of complex [PtH(IPr)2][SbF6] revealed its unsaturated nature, exhibiting a true T-shaped structure without stabilization by agostic interactions. Density functional theory calculations indicate that the binding and reaction of H2 in complexes [PtH(H2)(NHC) 2]+ is more favored for derivatives bearing aryl-substituted NHCs (IPr, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene and IMes = 1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene) than for those containing tert-butyl groups (ItBu). This outcome is related to the higher close-range steric effects of the ItBu ligands. Accordingly, H/D exchange reactions between hydrides [PtH(NHC)2]+ and D2 take place considerably faster for IPr and IMes* derivatives than for ItBu ones. The reaction mechanisms for both H2 addition and H/D exchange processes depend on the nature of the NHC ligand, operating through oxidative addition transition states in the case of IPr and IMes* or by a σ-complex assisted-metathesis mechanism in the case of ItBu.
AB - The reactivity toward H2 of coordinatively unsaturated Pt(II) complexes, stabilized by N-heterocyclic carbene (NHC) ligands, is herein analyzed. The cationic platinum complexes [Pt(NHC′)(NHC)]+ (where NHC′ stands for a cyclometalated NHC ligand) react very fast with H2 at room temperature, leading to hydrogenolysis of the Pt-CH 2 bond and concomitant formation of hydride derivatives [PtH(NHC)2]+ or hydrido-dihydrogen complexes [PtH(H 2)(NHC)2]+. The latter species release H 2 when these compounds are subjected to vacuum. The X-ray structure of complex [PtH(IPr)2][SbF6] revealed its unsaturated nature, exhibiting a true T-shaped structure without stabilization by agostic interactions. Density functional theory calculations indicate that the binding and reaction of H2 in complexes [PtH(H2)(NHC) 2]+ is more favored for derivatives bearing aryl-substituted NHCs (IPr, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene and IMes = 1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene) than for those containing tert-butyl groups (ItBu). This outcome is related to the higher close-range steric effects of the ItBu ligands. Accordingly, H/D exchange reactions between hydrides [PtH(NHC)2]+ and D2 take place considerably faster for IPr and IMes* derivatives than for ItBu ones. The reaction mechanisms for both H2 addition and H/D exchange processes depend on the nature of the NHC ligand, operating through oxidative addition transition states in the case of IPr and IMes* or by a σ-complex assisted-metathesis mechanism in the case of ItBu.
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U2 - 10.1021/ic500705t
DO - 10.1021/ic500705t
M3 - Article
C2 - 24716606
AN - SCOPUS:84899465895
SN - 0020-1669
VL - 53
SP - 4257
EP - 4268
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 8
ER -