1996
DOI: 10.1021/om950457v
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Synthesis and Nucleophilic Behavior of cis-[M(C6F5)2(Ph2PCHPPh2)]- (M = Pd, Pt):  C-Alkylation, Metalation, and Halogenation of Coordinated Bis(diphenylphosphino)methane. X-ray Crystal Structure of [Pt(C6F5)2(Ph2PCHIPPh2)]·C5H12

Abstract: The reaction of the neutral complexes cis-[M(C6F5)2(Ph2PCH2PPh2)] [M = Pd (1a), Pt (1b)] with LDA (lithium diisopropylamide) or LitBu (tert-butyllithium) in THF readily affords the anionic derivatives [M(C6F5)2(Ph2PCHPPh2)]- by deprotonation of the coordinated bis(diphenylphosphino)methane (dppm). The reactivity of the carbanionic center thus generated toward a variety of substrates has been studied. The reaction with alkyl halides such as MeI or EtI gives the neutral, C-alkylated complexes cis-[M(C6F5)2(Ph2PC… Show more

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Cited by 30 publications
(11 citation statements)
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“…[68] The Pt- . [69] The Pt-CH 3 [72] An almost identical distance [2.052(7) Å] was found for the Pt-Ph bond in the similar non-fluorinated compound [PtPh(κ 2 -2-C 6 H 4 PPh 2 )(PPh 3 )]. [73] The X-ray structure of trans-6 confirms the presence of monodentate trifluoroacetate, the Pt-O distance being 2.118(2) Å.…”
Section: Salts Cis-[ptlmentioning
confidence: 77%
“…[68] The Pt- . [69] The Pt-CH 3 [72] An almost identical distance [2.052(7) Å] was found for the Pt-Ph bond in the similar non-fluorinated compound [PtPh(κ 2 -2-C 6 H 4 PPh 2 )(PPh 3 )]. [73] The X-ray structure of trans-6 confirms the presence of monodentate trifluoroacetate, the Pt-O distance being 2.118(2) Å.…”
Section: Salts Cis-[ptlmentioning
confidence: 77%
“…An apparent symmetry plane coinciding with the coordination plane of the complex as in 1 and 3 will produce the same effect as a rotation in the spectra. [30][31][32] If the hemi-spaces above and below the coordination plane, which is set by the other ligands, are equivalent, so will the o-and m-F-atoms. 13 Or a dissociative mechanism: cytosine and methylcytosine (1-Mecyt) ligands on the other hand are known to easily dissociate in Pt and Pd complexes where free cytosine (in acetone-d 6 ) and an intermolecular exchange of cytosine between two molecules (in methanol-d 4 ) could by observed by NMR.…”
Section: Nmr Spectroscopymentioning
confidence: 99%
“…Bis(diphenylphosphino)methanide complexes have been commonly employed to synthesize polynuclear complexes in which the methanide acts as a tridentate ligand . The reactivity of the electron-rich carbon atom with nonmetallic electrophilic reagents has scarcely been studied, and only some C-alkylated, C-acylated, and C-halogenated diphenylphosphino derivatives (M = Cr, Fe, Mn, Mo, W, Pd, Pt) have been described . Recently, the activation of cyanogen by a manganese methanide compound, to give a tridentate (P,P,N) diphosphine, has been reported …”
Section: Introductionmentioning
confidence: 99%