On the Reactivity of Platina‐β‐diketone and Acetylplatinum(II) Complexes toward 2‐(Diphenylphosphanyl)benzaldehyde and Its Dioxolane Derivative. Issue 31 (16th September 2013)

• Record Type: Journal Article
• Authors: Kluge, Tim; Mendicute‐Fierro, Claudio; Bette, Martin; Rodríguez‐Diéguez, Antonio; Garralda, Maria A.; Steinborn, Dirk
• Is Part Of: European journal of inorganic chemistry. Issue 31(2013)
• Page Start: 5418
• Page End: 5427
• Publication Date: 2013-09-16
• Subjects: Platinum -- Ligand effects -- P, O ligands -- Hemiaminal ligands -- Schiff bases; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201300779
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The dinuclear platina‐β‐diketone [Pt2 {(COMe)2 H}2 (μ‐Cl)2 ] (1 ) reacts with four and two equivalents of 2‐[2‐(diphenylphosphanyl)phenyl]‐1, 3‐dioxolane (L1 ) to yield [Pt(COMe)Cl(PPh2 { o ‐C6 H4 CH(O2 C2 H4 )}‐κ P )2 ] (3 ) and [Pt(COMe)Cl(PPh2 { o ‐C6 H4 CH(O2 C2 H4 )}‐κ P, κ O )] (4 ), respectively. The weak Pt–O bond in4 can be easily broken up by stronger donors. Thus, complex4 reacts with PPh3 to yield [Pt(COMe)Cl(PPh3 )(PPh2 { o ‐C6 H4 CH(O2 C2 H4 )}‐κ P )] (5 ) and [Pt(COMe)Cl(PPh3 )2 ] (6 ) as well as withL1 to yield3 . Diacetylbis(amine)platinum(II) complexes cis ‐[Pt(COMe)2 (NH2 R)2 ] (R = Bn, 2a ; R = Et, 2b ; Bn = benzyl) react withL1 with the substitution of one amine ligand to yield [Pt(COMe)2 (NH2 R)(PPh2 { o ‐C6 H4 CH(O2 C2 H4 )}‐κ P )] (R = Bn, 7a ; R = Et, 7b ). The unprotected 2‐(diphenylphosphanyl)benzaldehyde (L2 ) reacts with the platina‐β‐diketone1 by oxidative C–H addition followed by reductive elimination of acetaldehyde to form [PtCl{PPh2 ( o ‐C6 H4 CO)‐κ P, κ C }{PPh2 ( o ‐C6 H4 CHO)‐κ P }] (8 ). On the other hand, the reactions of diacetylbis(amine)platinum(II) complexes2a /b andL2 proceeded with Schiff base formation and, thus, yielded complexes bearing hemiaminal–phosphane ligands, [Pt(COMe)2 (PPh2 { o ‐C6 H4 CH(OH)(NHR)}‐κ P, κ N )] (R = Bn, 9a ; R = Et, 9b ), and imine–phosphane ligands, [Pt(COMe)2 {PPh2 ( o ‐C6 H4 CH=NR)‐κ P, κ N }] (R = Bn, 10a ; R = Et, 10b ). The identities of all platinum complexes were unambiguously proved by microanalyses, high‐resolution mass spectrometric investigations, NMR ( 1 H, 13 C, 31 P, 195 Pt) and IR spectroscopy, and single‐crystal X‐ray diffraction analyses (for4, 9a ). The differences in the reactivity of the aldehyde–phosphaneL2 and its acetal‐protected derivativeL1 are discussed. Abstract : The reactions of diacetylbis(amine)platinum(II) complexes2 with the aldehyde–phosphane ligandL2 results in the formation of diacetylplatinum complexes10, which bear imine–phosphane ligands. Complexes9 with hemiaminal–phosphane ligands are intermediates. The analogous reactions with the acetal‐protected derivative ofL2 and with platina‐β‐diketones are also presented.