95532-51-7Relevant academic research and scientific papers
Carbon-oxygen bond formation at metal(IV) centers: Reactivity of palladium(II) and platinum(II) complexes of the [2,6-(dimethylaminomethyl) phenyl-N,C,N](Pincer) ligand toward lodomethane and dibenzoyl peroxide; structural studies of M(II) and M(IV) complexes
Canty, Allan J.,Denney, Melanie C.,Van Koten, Gerard,Skelton, Brian W.,White, Allan H.
, p. 5432 - 5439 (2008/10/09)
The presence of the [2,6-(dimethylaminomethyl)phenyl-N,C,N]- (pincer) ligand (NCN) in platinum(II) complexes has been used to generate stable organoplatinum(IV) complexes that model possible intermediates and reactivity in metal-catalyzed C-O bond formation processes. The complexes M(O 2CPh)(NCN) [M = Pd (1), Pt (2)] were obtained by metathesis reactions from the chloro analogues, and although 1 does not react with dibenzoyl peroxide, 2 does so to form Pt(O2CPh)3(NCN) (3) as a model intermediate for the acetoxylation of arenes by acetic acid in the presence of palladium(II) acetate and an oxidizing agent. The complex Pt(O 2CPh)(NCN) (2) reacts with iodomethane in a complex manner to form PtI-(NCN) (6) and cis-Pt(O2CPh)2Me(NCN) (7). Complex 7 decomposes to form Pt(O2CPh)(NCN) (2) and MeO2CPh, probably via benzoate dissociation followed by nucleophilic attack by the benzoate ion at the PtIV-Me carbon atom. The Pd(II) analogue Pd(O2CPh)(NCN) (1) reacts with Mel to give Pdl(NCN) (8) and MeO 2CPh, for which the potential intermediacy of Pd(IV) species could not confirmed by IH NMR spectroscopy. The complex PtTol(NCN) (4) (Tol = 4-tolyl) reacts with (PhCO2)2 to form cis-Pt(O 2CPh)2Tol(NCN) (5), but, unlike the PtIV^Me analogue 7, the PtIV^Tol complex 5 does not undergo facile C-O bond formation. X-ray structural studies of the isostructural square-planar complexes M(O2CPh)(NCN) (1, 2) and of the octahedral Pt(IV) complexes as solvates 3-l/2Me2CO, 5-Me2CO, and 7'Me2COH2O are reported. Complexes 5 and 7 have cis-PtC2 and cis-Pt(O 2CPh)2 configurations.
Synthesis and Structural Aspects of Rigid Aryl-palladium(II) and-Platinum(II) Complexes. X-ray Crystal Structure of o,o'-Bis(dimethylamino)methyl>phenylplatinum(II) Bromide
Terheijden, Jos,Koten, Gerard Van,Muller, Fred,Grove, David M.,Vrieze, Kees,et al.
, p. 401 - 418 (2007/10/02)
The tridentate monoanionic ligand o,o'-(Me2NCH2)2C6H3 (NCN') has been used to synthesize novel aryl-palladium(II) and -platinum(II) complexes and (M= Pt, Pd).Three synthetic procedures are described, namely: (i) reaction of the cationic complex + with KX or NaX to give (X= Cl, I, O2CH, NCS, NO2, NO3); (ii) displacement reactions using AgX with to give (X= CN, O3SCF3, O2CMe, O2CCF3) and (iii) transmetallation reactions of with organolithium to give (R= Ph, o-, m-, p-tolyl, CCPh, CC-p-tolyl).All the complexes have been characterized by elemental analysis IR, 1H NMR and 13C NMR spectroscopy.An X-ray diffraction study has shown that (2) has a square-planar structure, in which the tridentate ligand is bonded via C(ipso) (Pt-C 1.90(1) Angstroem, and two mutually trans-N donor atoms (Pt-N(1) 2.07(1), Pt-N(2) 2.09(1) Angstroem.The fourth site trans to C(ipso) is occupied by bromine (Pt-Br 2.526(2) Angstroem).The two chelate rings (N-Pt-C(ipso) 82.9(5) and 81.5(5) grade) are distinctly puckered, with the two NMe2 groups on opposite sides of the aryl plane.The Pt-C bond in 2 is shorter than analogous bonds in other arylplatinum(II) complexes, as a result of (i) the rigid structure of the tridentate ligand and (ii) the presence of two hard N donor atoms trans to one another across the platinum centre.
