60158-99-8Relevant articles and documents
An Adaptable Chelating Diphosphine Ligand for the Stabilization of Palladium and Platinum Carbenes
Barrett, Brittany J.,Iluc, Vlad M.
, p. 730 - 741 (2017/04/21)
Group 10 metal carbenes are proposed in catalytic transformations; however, their isolation remains difficult without the presence of a heteroatom donor. The adaptable cis and trans coordinating ligand PterP (1,2-bis(2-(diisopropylphosphino)phe
Reactions of coordinatively unsaturated platinum(II)-η1-allyl complexes with the electrophilic reagents sulfur dioxide, chlorosulfonyl isocyanate, and hexafluorophosphoric acid etherate
Hu, Yeh-Rom,Wojcicki, Andrew,Calligaris, Mario,Nardin, Giorgio
, p. 1561 - 1568 (2008/10/08)
New platinuma(II)-η1-allyl complexes of the type trans-(η1-C3H5)Pt(PR3) 2Cl (PR3 = PMe2Ph, P(i-Pr)3, P(t-Bu)3) have been synthesized by reaction of [(C3H5)PtCl]4 with 8 equiv of PR3. These and known complexes trans-(η1-C3H5)Pt(PR3) 2Cl (PR3 = PEt3, PCy3) and trans-(η1-CH2CH=CHMe)Pt(PEt3)2Cl have been investigated with respect to their behavior toward the electrophiles SO2, ClSO2NCO, and HPF6·Et2O. The complexes trans-(η1-C3H5)Pt(PR3) 2Cl react with SO2 in benzene solution at 25°C to afford trans-(CH2=CHCH2S(O)2)Pt(PR3) 2Cl, the order of reactivity as a function of PR3 being PEt3, PMe2Ph > P(i-Pr)3 > P(t-Bu)3 (no reaction). The crotyl isotopomers trans-(CH2CH=C*HMe)Pt(PEt3)2Cl (*H = H, D) insert SO2 with rearrangement of the η1-allyl fragment to give trans-(CH2=CHC*H(Me)S(O)2)Pt(PEt3) 2Cl. These sulfinato-S products were characterized by chemical analysis and IR and 1H and 31P{1H} NMR spectroscopy, and the structure of trans-(CH2=CHCH2S(O)2)Pt(PMe 2Ph)2Cl was determined by X-ray crystallography. Treatment of trans-(η1-C3H5)Pt(PR3) 2Cl (PR3 = PEt3, PCy3) and trans-(η1-CH2CH=CHMe)Pt(PEt3)2Cl with HPP6·Et2O in diethyl ether or toluene affords the η2-propene and η2-1-butene complexes [trans-(η2-CH2=CHMe)Pt(PR3) 2Cl]PF6 and [trans-(η2-CH2=CHEt)Pt(PEt3) 2Cl]PF6, respectively. The reactions with SO2 and HPF6·Et2O have been rationalized to proceed by attack of the electrophile at the allyl C=C; they appear to be analogous to the corresponding reactions of the 18-electron transition-metal-η1-allyl carbonyls and of related complexes. Treatment of trans-(η1-C3H5)Pt(PR3) 2Cl (PR3 = PEt3, P(i-Pr)3, PCy3) with ClSO2NCO in toluene at 25°C affords trans-Pt(PR3)2Cl2; in contrast, when these reactions are conducted at -78°C with gradual warming, trans-Pt(PR3)2Cl2 and/or another product, tentatively formulated as the cycloadduct trans-CH2N(SO2Cl)C(O)CH2CHPt(PR 3)2Cl, are obtained. The presumed cycloadduct could not be separated from trans-Pt(PR3)2Cl2 and was only characterized by 31P{1H} NMR spectroscopy and FAB mass spectrometry in the mixture. When L = PEt3, a precursor of trans-Pt(PEt3)2Cl2, possibly (η1-C3H5) Pt(PEt3)2Cl2(SO2NCO), is observed. The reactions with ClSO2NCO are provisionally explained by competing [3 + 2] cycloaddition and oxidative addition-reductive elimination pathways. Crystallographic data: monoclinic, space group P21/n, a = 10.633 (2) A?, b = 16.830 (4) A?, c = 13.745 (3) A?, β = 112.77 (2)°, Z = 4, R = 0.032, and Rw = 0.038.
Preparation, characterization, and some reactions of tri-tert-butylarsine complexes of platinum(II) and palladium(II) chlorides
Goel, Ram G.,Ogini, William O.,Srivastava, Ramesh C.
, p. 3611 - 3616 (2008/10/08)
As(t-Bu)3 reacts with platinum(II) chlorides to afford either trans-PtCl2[As(t-Bu)3]2 or the dinuclear complex Pt2(μ-Cl)2Cl2[As(t-Bu)3] 2. With palladium(II) chloride, however, only the dinuclear complex Pd2(μ-Cl)2Cl2[As(t-Bu)3] 2 is formed even in the presence of excess As(t-Bu)3. These complexes undergo substitution and/or bridge-cleavage reactions with CO, py, AsPh3, Cl-, or tertiary phosphines.
