Carbonylation of Hydrido–Phosphanido‐Bridged Dinuclear Platinum Complexes1. Issue 15 (27th April 2015)

• Record Type: Journal Article
• Authors: Latronico, Mario; Mastrorilli, Piero; Gallo, Vito; Todisco, Stefano; Dell'Anna, Maria Michela; Rizzuti, Antonino
• Is Part Of: European journal of inorganic chemistry. Issue 15(2015)
• Page Start: 2579
• Page End: 2586
• Publication Date: 2015-04-27
• Subjects: Carbonylation -- Platinum -- Phosphorus; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201500160
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The carbonylation of the solvento species [(PHCy2 )(L)Pt(μ‐PCy2 )(μ‐H)Pt(PHCy2 ){ κ P ‐P(OH)Cy2 }][BF4 ]2 ( Pt–Pt ) ([1 ‐L] 2+, L = CH2 Cl2, thf, CH3 CN) led to the formation of a singly bridged dicarbonyl Pt I compound syn ‐[(PHCy2 )(CO)Pt(μ‐PCy2 )Pt{ κ P ‐P(OH)Cy2 }(CO)] + ( Pt–Pt ) (2 + ). The reaction proceeded in two steps: 1) Substitution of L by CO to give the intermediate syn ‐[(PHCy2 )(CO)Pt(μ‐PCy2 )(μ‐H)Pt(PHCy2 ){ κ P ‐P(OH)Cy2 }] 2+ ( Pt–Pt ) ([1 ‐CO] 2+ ) and 2) uptake of a second molecule of CO and elimination of [PH2 Cy2 ] + (as the BF4 – salt) to give2 + . The dicarbonyl complex [2 ][BF4 ] was also synthesized starting from the dicyclohexylphosphanido‐bridged complex [(PHCy2 )Pt(μ‐PCy2 ){ κ 2 P, O ‐μ‐P(O)Cy2 }Pt(PHCy2 )]( Pt–Pt ) (5 ). In this case the first step consisted of the carbonylation of5 to give [(PHCy2 )2 Pt(μ‐PCy2 )Pt{ κ P ‐P(O)Cy2 }(CO)]( Pt–Pt ) (6 ), which was transformed into2 + by protonation with HBF4 under an atmosphere of CO. Prolonged reaction times for the carbonylation of [1 ‐L] 2+ in halogenated solvents resulted in the formation of the symmetrical dicarbonyl compound syn ‐[(CO)(PHCy2 )Pt(μ‐PCy2 )Pt(PHCy2 )(CO)] + ( Pt–Pt ) (3 + ) along with Cy2 P(H)OBF3 . Complexes6 and [1 ‐L][BF4 ]2 were also formed by the carbonylation of5 and [1 ‐OMe2 ][BF4 ]2 in the solid state. Abstract : The singly bridged dicarbonyl Pt I compound2 + can be obtained, both in solution and in the solid state, either by carbonylation of the solvento species [1‐ L] 2+ or by carbonylation of5 followed by the addition of HBF4 .