The octaphosphine {cyclo-(P4tBu3)}2 (1) possesses a multifaceted coordination chemistry. The predominant binding mode is a P,P-chelate, e.g., in the monometallic chelate complex [MLL′(1-κ2P2,P4′)] in which the ligand 1 adopts a gauche conformation. Examples include square-planar (M = RhI, L = CO, L′ = Cl (2), M = PdII, L = L′ = Cl (3), M = PtII, L = L′ = Cl (9)), tetrahedral (M = Co-I, L = NO, L′ = CO (4)), and trigonal-planar complexes [ML(1-κ2P2,P4′)] (M = Pd0, L = PPh3, (5), M = CuI, L = Br (6)). With 2 equiv of [CuBr(SMe2)], a dinuclear complex [(CuBr)2(1-κ2P2,P2′,κ2P4,P4′)] (7) was obtained which features a synperiplanar conformation of the octaphosphine. A second coordination mode was also observed in [PtCl2(1-κ2P1,P2′)] (10) in which the bridge phosphorus atom in octaphosphine 1 is involved in the chelation, with the ligand in an antiperiplanar conformation. Thermolysis of selected complexes showed them to be suitable candidates for the generation of phosphorus-rich metal phosphides MPx (x > 1).

Versatile Coordination Chemistry of Hexa- tert-butyl-octaphosphine / T. Grell, E. Hey-Hawkins. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 59:11(2020 Jun 01), pp. 7487-7503. [10.1021/acs.inorgchem.0c00262]

Versatile Coordination Chemistry of Hexa- tert-butyl-octaphosphine

T. Grell
Primo
;
2020-06-01

Abstract

The octaphosphine {cyclo-(P4tBu3)}2 (1) possesses a multifaceted coordination chemistry. The predominant binding mode is a P,P-chelate, e.g., in the monometallic chelate complex [MLL′(1-κ2P2,P4′)] in which the ligand 1 adopts a gauche conformation. Examples include square-planar (M = RhI, L = CO, L′ = Cl (2), M = PdII, L = L′ = Cl (3), M = PtII, L = L′ = Cl (9)), tetrahedral (M = Co-I, L = NO, L′ = CO (4)), and trigonal-planar complexes [ML(1-κ2P2,P4′)] (M = Pd0, L = PPh3, (5), M = CuI, L = Br (6)). With 2 equiv of [CuBr(SMe2)], a dinuclear complex [(CuBr)2(1-κ2P2,P2′,κ2P4,P4′)] (7) was obtained which features a synperiplanar conformation of the octaphosphine. A second coordination mode was also observed in [PtCl2(1-κ2P1,P2′)] (10) in which the bridge phosphorus atom in octaphosphine 1 is involved in the chelation, with the ligand in an antiperiplanar conformation. Thermolysis of selected complexes showed them to be suitable candidates for the generation of phosphorus-rich metal phosphides MPx (x > 1).
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/906724
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