The reactivity of dichloroplatinum(II) complexes containing thioether-functionalized bis(diphenylphosphanyl)amines of formula (Ph2P)2N(CH2)2SR (R = (CH2)5CH3, CH2Ph) toward group 6 carbonylmetalates Na[M(CO)3Cp] (M = Mo or W, Cp = cyclopentadienyl) was explored. Reactions with two or more equivalents of Na[M(CO)3Cp] (M = Mo or W) afforded the trinuclear complexes of general formula [PtPh{M(CO)3Cp}{μ-P(Ph)N(CH2CH2SR)(PPh2)-κ3P,P,S}M(CO)2Cp] (3 M = Mo, R = (CH2)5CH3; 4 M = Mo, R = CH2Ph; 9 M = W, R = (CH2)5CH3; 10 M = W, R = CH2Ph), the structure of which consists of a six-membered platinacycle condensed with a four-membered tiebar above startM–P–N–tiebar above endP cycle, together with small amounts of isomeric PtM2 clusters [PtM2(CO)5Cp2{(Ph2P)2N(CH2CH2SR)-κ2P,P}] (5 M = Mo, R = (CH2)5CH3; 6 M = Mo, R = CH2Ph; 11 M = W, R = (CH2)5CH3; 12 M = W, R = CH2Ph) in which the ligand (Ph2P)2NR solely chelates the Pt atom or bridges an M–Pt bond as in [PtM2(CO)5Cp2{μ-(Ph2P)2N(CH2CH2SR)-κ2P,P}] (7 M = Mo, R = (CH2)5CH3; 8 M = Mo, R = CH2Ph; 13 M = W, R = (CH2)5CH3; 14 M = W, R = CH2Ph). The synthesis of the trinuclear complexes 3, 4, 9, and 10 entails an unexpected P-phenyl bond cleavage reaction and phenyl migration onto Pt. When only 1 equiv of Na[M(CO)3Cp] (M = Mo or W) was used, the heterodinuclear products of monosubstitution [PtCl{M(CO)3Cp}{Ph2PN(R)PPh2-P,P}] (15 M = Mo, R = (CH2)5CH3; 16 M = Mo, R = CH2Ph; 17 M = W, R = (CH2)5CH3; 18 M = W, R = CH2Ph) were obtained, which are the precursors to the bicyclic products 3, 4, 9, and 10, respectively. Density functional calculations were performed to study the thermodynamics of the formation of all the new complexes, to evaluate the relative stabilities of the isomeric chelated and bridged forms, and to trace the mechanism of formation of the phosphanido-bridged products 3, 4, 9, and 10. It was concluded that Pt(II) complexes containing a thioether-functionalized short-bite ligand, [PtCl2{Ph2PN(R)PPh2}], react with Na[M(CO)3Cp] to yield first heterodinuclear Pt–M and then heterotrinuclear PtM2 complexes resulting from the activation of a P–C bond in one of the PPh2 groups and phenyl migration to Pt. The critical role of an intramolecular thioether group was demonstrated.

Sulfur-Assisted Phenyl Migration in PtW2 and PtMo2 Clusters Containing Thioether-Functionalized Bis(diphenylphosphanyl)amines / Todisco, S.; Mastrorilli, P.; Latronico, M.; Gallo, V.; Englert, U.; Re, N.; Creati, F.; Braunstein, P.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 54:10(2015), pp. 4777-4798. [10.1021/acs.inorgchem.5b00223]

Sulfur-Assisted Phenyl Migration in PtW2 and PtMo2 Clusters Containing Thioether-Functionalized Bis(diphenylphosphanyl)amines

Todisco, S.;Mastrorilli, P.
;
Latronico, M.;Gallo, V.;
2015-01-01

Abstract

The reactivity of dichloroplatinum(II) complexes containing thioether-functionalized bis(diphenylphosphanyl)amines of formula (Ph2P)2N(CH2)2SR (R = (CH2)5CH3, CH2Ph) toward group 6 carbonylmetalates Na[M(CO)3Cp] (M = Mo or W, Cp = cyclopentadienyl) was explored. Reactions with two or more equivalents of Na[M(CO)3Cp] (M = Mo or W) afforded the trinuclear complexes of general formula [PtPh{M(CO)3Cp}{μ-P(Ph)N(CH2CH2SR)(PPh2)-κ3P,P,S}M(CO)2Cp] (3 M = Mo, R = (CH2)5CH3; 4 M = Mo, R = CH2Ph; 9 M = W, R = (CH2)5CH3; 10 M = W, R = CH2Ph), the structure of which consists of a six-membered platinacycle condensed with a four-membered tiebar above startM–P–N–tiebar above endP cycle, together with small amounts of isomeric PtM2 clusters [PtM2(CO)5Cp2{(Ph2P)2N(CH2CH2SR)-κ2P,P}] (5 M = Mo, R = (CH2)5CH3; 6 M = Mo, R = CH2Ph; 11 M = W, R = (CH2)5CH3; 12 M = W, R = CH2Ph) in which the ligand (Ph2P)2NR solely chelates the Pt atom or bridges an M–Pt bond as in [PtM2(CO)5Cp2{μ-(Ph2P)2N(CH2CH2SR)-κ2P,P}] (7 M = Mo, R = (CH2)5CH3; 8 M = Mo, R = CH2Ph; 13 M = W, R = (CH2)5CH3; 14 M = W, R = CH2Ph). The synthesis of the trinuclear complexes 3, 4, 9, and 10 entails an unexpected P-phenyl bond cleavage reaction and phenyl migration onto Pt. When only 1 equiv of Na[M(CO)3Cp] (M = Mo or W) was used, the heterodinuclear products of monosubstitution [PtCl{M(CO)3Cp}{Ph2PN(R)PPh2-P,P}] (15 M = Mo, R = (CH2)5CH3; 16 M = Mo, R = CH2Ph; 17 M = W, R = (CH2)5CH3; 18 M = W, R = CH2Ph) were obtained, which are the precursors to the bicyclic products 3, 4, 9, and 10, respectively. Density functional calculations were performed to study the thermodynamics of the formation of all the new complexes, to evaluate the relative stabilities of the isomeric chelated and bridged forms, and to trace the mechanism of formation of the phosphanido-bridged products 3, 4, 9, and 10. It was concluded that Pt(II) complexes containing a thioether-functionalized short-bite ligand, [PtCl2{Ph2PN(R)PPh2}], react with Na[M(CO)3Cp] to yield first heterodinuclear Pt–M and then heterotrinuclear PtM2 complexes resulting from the activation of a P–C bond in one of the PPh2 groups and phenyl migration to Pt. The critical role of an intramolecular thioether group was demonstrated.
2015
Sulfur-Assisted Phenyl Migration in PtW2 and PtMo2 Clusters Containing Thioether-Functionalized Bis(diphenylphosphanyl)amines / Todisco, S.; Mastrorilli, P.; Latronico, M.; Gallo, V.; Englert, U.; Re, N.; Creati, F.; Braunstein, P.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 54:10(2015), pp. 4777-4798. [10.1021/acs.inorgchem.5b00223]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11589/1406
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