title: Coordination of bis(azol-1-yl)methane-based bisphosphines towards RuII, RhI, PdIIand PtII: synthesis, structural and catalytic studies.
abstract: The coordination chemistry of bisphosphine ligands assembled on the five-membered heterocyclic platform of bis(azol-1-yl)methane viz.: bis(2-diphenylphosphinoimidazol-1-yl)methane (1), bis(5-diphenylphosphinopyrazol-1-yl)methane (2) and bis(5-diphenylphosphino-1,2,4-triazol-1-yl)methane (3) with RuII, RhI, PdIIand PtIIis described. The bisphosphines 1-3 react with elemental selenium to give the corresponding bis-selenoyl derivatives 4-6. The reactions of 1-3 with transition metal derivatives produce complexes with different coordination modes. Bisphosphine 1 showed a preference for the κ2-P,P mode of coordination, whereas bisphosphines 2 and 3, besides the κ2-P,P mode also showed a head-to-tail κ2-P,N coordination mode resulting in the formation of binuclear complexes [Rh2(COD)2{(CH2(1,2-C3H2N2PPh2)2)-κ2P,N}][BF4]2(14), [Rh2(COD)2{(CH2(1,2,4-C2HN3PPh2)2)-κ2P,N}][BF4]2(15), [Pd2(η3-C3H5)2{(CH2(1,2-C3H2N2PPh2)2)-κ2P,N}][BF4]2(21) and [Pd2(η3-C3H5)2{(CH2(1,2,4-C2HN3PPh2)2)-κ2P,N}][BF4]2(22). Several of these complexes have also been structurally characterized. The in situ generated RhIcomplex of bisphosphine 1 showed moderate to good selectivity in the hydroformylation of various styrene derivatives.
authors.affiliation: Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India. krishna@chem.iitb.ac.in msb_krishna@iitb.ac.in.
authors.forename: Sajad A
authors.initials: SA
authors.lastname: Bhat
authors.affiliation: Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India. krishna@chem.iitb.ac.in msb_krishna@iitb.ac.in.
authors.forename: Madhusudan K
authors.initials: MK
authors.lastname: Pandey
authors.affiliation: Department of Chemistry, Tulane University, New Orlens, Louisiana 70118, USA.
authors.forename: Joel T
authors.initials: JT
authors.lastname: Mague
authors.affiliation: Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India. krishna@chem.iitb.ac.in msb_krishna@iitb.ac.in.
authors.forename: Maravanji S
authors.identifier: http://orcid.org/0000-0003-3736-6148
authors.initials: MS
authors.lastname: Balakrishna