22853-55-0Relevant academic research and scientific papers
Some mixed transition metal compounds of 1,3-diyne with metallacycles derived by cross-coupling of alkynyl ligands and sequential C-C bond coupling between 1,3-diyne and carbon monoxide
Yamazaki, Shinsaku,Taira, Zenei,Yonemura, Toshiaki,Deeming, Anthony J.
, p. 20 - 27 (2008/10/09)
By treating cis-Pt(C≡CPh)2(dppe) (1) with Mn 2(CO)9(CH3CN) in refluxing toluene, cross-coupling of alkynyl ligands occurs to afford mixed transition metal compound of 3,4-diphenyl-1,3-butadiyne, [Mn2Pt(μ3-η 1:η1:η2:η4 - PhCCCCPh)(CO)6(dppe)] (2) in 19-38% isolated yield. 2 has a structure formed by an unprecedented heterometal complexation of 1-manganacyclo-2,3,4-pentatriene. The Pt(II) acetylide, by treating with Ru 3(CO)9(PPh3)3, directly converts into a π-complex of 1,3-diyne, Pt(η2-PhCCCCPh)(dppe) (4), in 38% yield. By reacting π-alkyne compound Pt(η 2-PhCC-C≡CPh)(PPh3)2 with Fe(CO) 5 and Ru3(CO)12, bimetallic [FePt(μ 3-1:η1:η2-COC 4Ph2)(CO)3(PPh3)2] (5a) and triangular cluster [MPt2(μ3-η 1:η1:η2-PhCC-C≡CPh)-(CO) 2(PPh3)2] (6a) have successionally been isolated in considerable yields. A dimetallic analogue of alkyne [FePt{μ 2-η1:η1:η2-C(O)C 2H2}(CO)3(Ph3)2] (5b) and trimetallic [MPt2(μ3-η1:η 1:η2-R1CCR2)(CO) 7-n(PPh3)n] (6b-f) {R1 = Ph, R 2 = C=CPh, n = 3, M = Fe, 6b; R1 = R2 = H, n = 3, M = Fe, 6c; R1 = R2 = Ph, n = 2, M = Fe, 6d and iso-6d; R1 = R2 = OCOCH3, n = 2, M = Fe, 6e; M = Ru, 6f} have consecutively been prepared. Crystal structures of five of the compounds have been determined.
Reactions of binuclear ruthenium-platinum μ-allenyl complexes with nucleophilic and electrophilic reagents. The characterization of two 1:1 adducts of L(PPh3)Pt(μ-η1:η2α,β-C(Ph)=C=CH2)Ru(CO)Cp (L=PPh3, t-BuNC) and p-toluenesulfonyl isocyanate
Willis, Richard R.,Calligaris, Mario,Faleschini, Paolo,Gallucci, Judith C.,Wojcicki, Andrew
, p. 465 - 478 (2007/10/03)
Reactions of (PPh3)2Pt(μ-η1:η2α,β-C(R)=C=CH2)Ru(CO)Cp (R=H (1), Ph (2)) with Ph2PCH2CH2CH2PPh2, PEt3 and t-BuNC in THF at -78°C to room temperature afforded the substitution products L2Pt(μ-η1:η2α,β-C(R)=C=CH2)Ru(CO)Cp (R=H, L2=Ph2PCH2CH2CH2PPh2 (3), R=Ph, L2=Ph2PCH2CH2CH2PPh2 (4), R=H, L2=2PEt3 (5), R=Ph, L2=PPh3 and t-BuNC (6)). No reaction was observed for 1 with Et2NH or C6H11NH2 and 2 with p-TolS(O)2NH2 in THF at reflux temperature. Complex 2 reacted with p-TolS(O)2NCO (TSI) in toluene at -78°C to room temperature to yield two 1:1 addition products of the reactants: the γ-carbon substituted μ-allenyl (PPh3)2Pt(μ-η1:η2α,β-C(Ph)=C=CHC(O)NHS(O)2Tol-p) (7) and the [3+2] cycloadduct (PPh3)2Pt(μ-η1:η2-C=C(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (8). Complexes 4 and 6 afforded with TSI, under essentially similar conditions, only [3+2] cycloadducts, L2Pt(μ-η1:η2-C=C(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (L2=Ph2PCH2CH2CH2PPh2 (9), PPh3 and t-BuNC (10)). All products were characterized by a combination of IR and NMR (1H, 13C{1H} and 31P{1H}) spectroscopy, FAB MS and elemental analysis. The structures of 7 (as 7·C3H6O) and 10 were determined by single-crystal X-ray diffraction analysis. Reactions of 2 with trans-NCCH=CHCN (L) and of 1 with the alkynes MeO2CC?CCO2Me, MeO2CC?CMe, PhC?CH and PhC?CPh (L) resulted in the formation of the mononuclear metal complexes Cp(CO)2RuC(R)=C=CH2 (R=H, Ph) and (PPh3)2PtL. The reverse of this fragmentation reaction occurred when Cp(CO)2RuCH=C=CH2 was treated with (PPh3)2Pt(PhC?CPh). No reaction was observed between 2 and each (CN)2C=CPh2 and MeS(O)2NSO in benzene or toluene on heating. The η1-allenyl Cp(CO)2RuC(Ph)=C=CH2, obtained in this study, is a new compound.
A Laser Flash Photolysis Study of Transient Bis(triphenylphosphine)platinum(0)
Oishi, Shigero,Suzuki, Keita
, p. 171 - 172 (2007/10/02)
Transient spectra were obtained for bis(triphenylphosphine)platinum(0) (ε410: 630 dm3mol-1cm-1), to which O2 and diphenylacetylene coordinated with second-order rate constants of 2.4x104 and 1.2x106 dm3mol-1s-1 respectively.
Electrochemical generation and reactivity of bis(tertiary phosphine)platinum(0) complexes: A comparison of the reactivity of [Pt(PPh3)2] and [Pt(PEt3)2] equivalents
Davies, Julian A.,Eagle, Cassandra T.,Otis, Deborah E.,Venkataraman, Uma
, p. 1080 - 1088 (2008/10/08)
Electrochemical reduction of cis-[PtCl2(PR3)2] (R = Ph, Et) in CH3CN/C6H6 containing NBu4ClO4 at a Hg pool electrode generates [Pt(PR3)2] equivalents in solution. Where R = Ph, the [Pt(PR3)2] equivalent may be trapped by O2, O2/CO2, HCl, MeI, C6H5COCl, and RC≡CR (R = Ph, COOMe) but not by the less reactive substrate PhCl. Where R = Et, the [Pt(PR3)2] equivalent reacts with the NBu4+ cation to ultimately generate trans-[PtH(Cl)(PEt3)2]. Prolonged electrolyses cause reduction of trans-[PtH(Cl)(PEt3)2] leading to hydride attack on the CH3CN solvent and ultimately forming trans-[PtH(CH2CN)(PEt3)2]. In the presence of bases such as NBu3, trans-[PtH(CH2CN)(PEt3)2] is isomerized in CH3CN solution producing trans-[PtCN(CH3)(PEt3)2]. The use of electroinactive trapping agents such as PhCl or PhCN as cosolvents for the reduction of cis-[PtCl2(PEt3)2] allows trapping of the [Pt(PEt3)2] equivalents as trans-[PtPh-(X)(PEt3)2] (X = Cl, CN).
Photoisomerism of (dimethyl acetylenedicarboxylate)bis(triphenylphosphine)-platinum. Structure of (ethoxycarbonyl)((methoxycarbonyl)-acetylido)bis(triphenylphosphine)platinum(II)
Kubota, Mitsuru,Sly, William G.,Santarsiero, Bernard D.,Clifton, Maurice S.,Kuo, Louis
, p. 1257 - 1259 (2008/10/08)
The photolysis of [Pt(PPh3)2(RC≡CX)] gives the acetylido complex [Pt(Ph3P)2R(C≡CX)] for R = X = CH3O(CO), but similar photoisomerization does not occur for complexes of acetylenes with R = X = Ph or CH2OH or C(CH3)2OH and R = H and X = CH2OH or CO2H or CH2NH2. The molecular structure of the acetylido complex [Pt(Ph3P)2((CO)OEt)(C≡C(CO)OCH3)] was determined by X-ray diffraction using 6617 reflections: triclinic, P1, a = 11.069 (3) ?, b = 13.420 (3) ?, c = 14.242 (3) ?, α = 102.27 (2)°, β = 105.85 (2)°, γ = 104.01 (2)°, Z = 2. The Pt-C bond lengths are 1.991 (8) ? (to (methoxycarbonyl)acetylide) and 2.024 (8) ? (to ethoxycarbonyl), and the Pt-P bond lengths are 2.298 (2) and 2.347 (2) ?.
Electrochemical generation and reactivity of bis(triphenylphosphine)platinum(0): An electrosynthesis of platinum-acetylene complexes
Davies, Julian A.,Eagle, Cassandra T.,Otis, Deborah E.,Venkataraman, Uma
, p. 1264 - 1266 (2008/10/08)
Controlled potential bulk reductive electrolysis of cis-[PtCl2(PPh3)2] results in the generation of [Pt(PPh3)2] in solution. This 2-coordinate, 14-electron compound is efficiently trapped by acetylene
