Enhancing Reactivity of Directly íObservable B–H–Pt Interactions through Conformational Rigidity. Issue 15 (3rd February 2016)

• Record Type: Journal Article
• Authors: Pal, Shrinwantu; Drover, Marcus W.; Patrick, Brian O.; Love, Jennifer A.
• Other Names: Pettinari C. guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 15/16(2016)
• Page Start: 2403
• Page End: 2408
• Publication Date: 2016-02-03
• Subjects: Scorpionate ligands -- Platinum -- Agostic interactions -- B–H functionalization; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501305
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : We report for the first time the direct syntheses of trimethylplatinum(IV) complexes supported by bis(pyrazolyl)dihydridoborate (Bp) and bis(3, 5‐dimethylpyrazolyl)dihydridoborate (Bp*) ligands from the corresponding dimethylplatinum(II) complexes. X‐ray crystallographic and multinuclear NMR characterization of the trimethylplatinum(IV) complexes reveal agostic B–H–Pt interactions. Solid‐state analysis reveals that BpPt IV Me3 adopts a dinuclear structure featuring an intermolecular B–H–Pt bridge, whereas Bp*Pt IV Me3 adopts a mononuclear structure containing an intramolecular B–H–Pt bridge. Addition of acetonitrile leads to cleavage of the weakly coordinating B–H–Pt interactions, and in the case of Bp*Pt IV Me3, leads to hydroboration of acetonitrile. The B–H fragment interacting with the Pt IV center in Bp*Pt IV Me3 was also found to react with methanol to form a methoxy‐bridged complex. DFT calculations were employed to investigate the structural contributions to the difference in the reactivity of the Bp‐ and Bp*‐supported complexes. Abstract : Trimethylplatinum(IV) complexes featuring agostic B–H–Pt interactions supported by bis(pyrazolyl)borate (Bp) and bis(3, 5‐dimethylpyrazolyl)borate (Bp*) ligands show interesting structural differences both in solution and the solid state. These differences result in enhanced reactivity of the Bp* complexes towards hydroboration of acetonitrile and protonolysis with methanol.