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• W2045647923 abstract "Three new bis(7-azaindol-1-yl)methane (BAM) derivative ligands Me3Si-BAM (1a), Me3Sn-BAM (1b), and Ph3Sn-BAM (1c) have been synthesized, and their reactivities with [PtR2(μ-SMe2)]n (R = Me, Ph) have been examined. Two Pt(II) complexes Pt(Me3Si-BAM)R2 (R = Me, 2; Ph, 3) were obtained from the reactions of 1a. The reactions of 1b with [PtR2(μ-SMe2)]n (R = Me, Ph) produced unexpected novel N,C,N-BAM Pt(IV) complexes Pt(N,C,N-BAM)(SnMe3)R2 (R = Me, 4; Ph, 6) likely via oxidative cleavage of the CBAM−Sn bond in 1b. 1c reacted with [PtPh2(μ-SMe2)]n (n = 2, 3) yielding the anticipated Pt(II) complex Pt(Ph3Sn-BAM)Ph2 (7), whereas its reaction with [PtMe2(μ-SMe2)]2 resulted in unusual PtII-Me and SnIV-Ph metathesis, yielding also 7 as one of the products. Mechanistic investigation was carried out to understand this phenomenon. The reactivities of 2 with MeI, MeOTf, and I2 were examined. Its reaction with I2 gave rise to Pt(Me3Si-BAM)I2 (9) along with CH3I, indicating the possibility of functionalizing PtII-Me via iodinolysis. The reaction of Pt(N,C,N-BAM)(SnMe3)Me2 (4) with I2 produced a number of unusual N,C,N-BAM Pt(IV) complexes including Pt(N,C,N-BAM)Me(I)(SnI2Me) (13) and Pt(N,C,N-BAM)Me(I)(I3) (14) due to the electrophilic cleavage of the Sn-Me, Pt-Me and/or Pt−Sn bond(s) by I2. For comparison, we also investigated the reaction of Pt(N,C,N-BAM)Me3 (M1) with I2 which was found to exhibit a high regioselectivity for the axial Pt-Me group, resulting in Pt(N,C,N-BAM)Me2(I3) (15) with the two Pt-Me being cis to each other. The reactions of 4 and M1 with I2 are rare examples of PtIV−CH3 bond cleavage by the elimination of CH3I. The structures of 1a and complexes 2, 7, 9, and 13−15 were determined by X-ray diffraction analyses." @default.
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• W2045647923 date "2009-04-01" @default.
• W2045647923 modified "2023-10-18" @default.
• W2045647923 title "Reactivity of SiMe₃- and SnR₃-Functionalized Bis(7-azaindol-1-yl)methane with [PtR₂(μ-SMe₂)]_<i>n</i> (R = Me, Ph) and the Resulting Pt(II) and Pt(IV) Complexes" @default.
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• W2045647923 doi "https://doi.org/10.1021/om900022n" @default.
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