16841-99-9Relevant academic research and scientific papers
Heterometallic complexes with borole ligands
Braunstein, Pierre,Englert, Ulli,Herberich, Gerhard E.,Neuschuetz, Mark,Schmidt, Martin U.
, p. 2807 - 2812 (1999)
The borole-containing carbonylmetalates [(η-C4H4BPh)Re(CO)3]- ([Re]-) and [(η-C4H4BPh)Fe(CO)2H]- ([Fe]-) were used for the synthesis of heterometallic complexes with Re-Hg, Re-Cu, Re-Ag, Re-Au or Fe-Pt metal-metal bonds, respectively. The complex [Re]-Hg-[Re] 1 was characterized by X-ray diffraction and contains a linear metal chain. In the presence of HgCl2, redistribution reactions were observed, leading to [Re]-Hg-Cl 2 which was independently prepared from [Re]- and an excess of HgCl2. The reaction of [Fe]- with trans-[PtBr2(4-Mepy)2] (4-Mepy = 4-methylpyridine) afforded the trinuclear complex trans-[Pt[Fe]2(4-Mepy)2] 6 which was characterized by X-ray diffraction and contains two hydrido ligands which bridge the Fe-Pt bonds.
Reactions and electrochemical behaviour of dithiocarbene complexes of platinum(II)
Belluco, Umberto,Bertani, Roberta,Michelin, Rino A.,Mozzon, Mirto,Silva, M. Fatima C. Guedes da,et al.
, (1995)
The dithiocarbene complex trans-[(PPh3)2PtH{C(SMe)2}][BF4] (1) was obtained from the reaction of trans-[(PPh3)2PtH(CF3)] with CH3SH in the presence of ethereal HBF4. The reactions of 1 with different nucleophiles, such as Cl(-), H(-) and CN(-) ions, P-don
Synthesis of TiRu2 heterobimetallic and TiRuM (M = Rh, Ir, Pd, Pt) heterotrimetallic sulfido clusters from a hydrosulfido-bridged titanium-ruthenium complex
Kuwata,Kabashima,Sugiyama,Ishii,Hidai
, p. 2034 - 2040 (2001)
Treatment of the hydrosulfido-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti(μ2-SH)2RuCl (η5-C5Me5)] (1; Cp = η5-C5H5) with an excess of triethylamine followed by addition of [RuCl2(PPh3)3] and [{(cod)M}2-(μ2-Cl)2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to the formation of the TiRu2 and TiRuM mixed-metal sulfido clusters [(CpTi){(η5-C5Me5)Ru}{Ru (PPh3)2}(μ3-S)2 (μ2-Cl)2] (3) and [(CpTi){η5-C5Me5)Ru}{M(cod)}- (μ3-S)2(μ2-Cl)] (M = Rh (4a), Ir (4b)), respectively. On the other hand, the reactions of 1 with [M(PPh3)4] (M = Pd, Pt) afforded the TiRuM trinuclear clusters [(CpTiCl){(η5-C5Me5)Ru}{M (PPh3)2}(μ3-S)(μ2-S) (μ2-H)] (M = Pd (5a), Pt (5b)) with an unprecedented M3(μ3-S)(μ2-S) core. The detailed structures of these triangular clusters 3-5 have been determined by X-ray crystallography. Crystal data: 3, triclinic, P1, a = 12.448(4) A, b = 12.773-(4) A, c = 17.270(4) A, α = 100. 16(2)°, β = 99.93(2)°, γ = 114.11(3)°, V = 2373(1) A3, Ζ = 2; 4a, triclinic, P1, a = 7.714(2) A, b = 11.598(3) A, c = 14.802(4) A, α = 80.46(2)°, β = 82.53(2)°, γ = 71.47(2)°, V = 1234.0(6) A3, Z = 2; 4b, triclinic, P1, a = 7.729(1) A, b = 11.577(2) A, c = 14.766(3) A, α = 80.14(1)°, β = 82.71(1)°, γ = 71.55(1)°, V = 1231.1(4) A3, Ζ = 2; 5a, monoclinic, P21/c, a = 11.259(4) A, b = 16.438(4) A, c = 26.092(5) A, β = 102.23(3)°, V = 4719(2) A3, Z = 4; 5b, monoclinic, P21/n, a = 11.369(2) A, b = 16.207-(3) A, c = 26.116(2) A, β = 102.29(1)°, V = 4701(1) A3, Ζ = 4.
Novel ketene formation by reactions of acid chlorides with low-valent platinum complexes
Ishii, Youichi,Kobayashi, Yoshihiro,Iwasaki, Masakazu,Hidai, Masanobu
, p. 133 - 140 (1991)
Pt(CO)n(PPh3)4-n (n = 0-2) reacts with Ph2CHCOCl under CO to afford diphenylketene and trans-PtHCl(PPh3)2.For this reaction, the rate law is zero order in the platinum complex, first order in Ph2CHCOCl, and first order in free PPh3.A primary isotope effect (kH/kD = 4.5) was observed in the reaction of Ph2CDCOCl.A mechanism is proposed which involves the rate-determining enolization of Ph2CHCOCl by PPh3 followed by fast abstraction of HCl by a platinum(0) complex.
Diplatinum complexes: Chemoselective reactions of the μ-orthometalated, metal-metal bonded complex
Archambault, Christine,Bender, Robert,Dusausoy, Yves,Welter, Richard,Braunstein, Pierre
, p. 545 - 552 (2013/06/26)
In order to investigate further the chemoselectivity of reactions involving the μ-orthometalated, metal-metal bonded dinuclear Pt(I) complex [Pt 2(μ-o-C6H4PPh2)(μ-PPh 2)(PPh3)2](Pt-Pt) (1), it was reacted with HCl and HI using various stoichiometries. The first step was the breaking of the metal-carbon bond and the formation of C-H and Pt-X bonds. When a 1:1 ratio was used, the complexes [Pt2X(μ-PPh2)(PPh3) 3](Pt-Pt) (2, X = Cl; 3, X = I) have been obtained but the use of a 2:1 ratio resulted instead in the formation of the complexes [Pt 2(μ-H)(μ-PPh2)X2(PPh3) 2](Pt-Pt) (4, X = Cl; 6, X = I). The latter transformed into [Pt 2(μ-X)(μ-PPh2)X2(PPh3) 2] (5, X = Cl; 7, X = I) in the presence of an additional equivalent of HX. The cis,cis- and cis,trans-isomers of 7 were also obtained by oxidation of 3 with one equivalent of iodine. Whereas compounds 4, cis,cis-5, and cis,trans-7 have been characterized in solution, the complexes 2·1/2C7H8, 3, 6 and cis,cis-7 have been isolated and structurally characterized by X-ray diffraction.
Reactions of free radicals with η3-allylpalladium(II) complexes: Cyclohexyl radicals
Reid, Simon J.,Baird, Michael C.
, p. 1257 - 1264 (2007/10/03)
Allyl palladium complexes of the types [(η3-allyl)PdCl] 2, (η3-allyl)PdCl(PPh3) and [(η3-allyl)Pd(PPh3)2]Cl (allyl=C3H5, 1-MeC3H4, 2-MeC3H4, 1-PhC3H4, 2-PhC3H4) react with cyclohexyl radicals derived from the visible light photolysis of (c-hex)Co(DMG)2(py). The reactions proceed via initial attack of the free radical at the metal center, followed by β-hydrogen elimination and subsequent reductive elimination of propene, 1-butene, isobutene, 3-phenylpropene and 2-phenylpropene, respectively. The 3-phenylpropene can be catalytically isomerized to the thermodynamically more stable 1-phenylpropene by either palladium metal or palladium(0) products, but the formation of 1-butene and 3-phenylpropene as primary products is unusual. A mechanism, differing in many ways from that proposed previously for analogous reactions of phenyl and trityl radicals, is proposed for the overall reaction and supported by use of the labeled cobaloxime, (2,2,6,6-D4-c-hex)Co(DMG)2(py).
Transition metal complexes incorporating the BF2 ligand formed by oxidative addition of the B-B bond in B2F4
Lu, Norman,Norman, Nicholas C.,Guy Orpen,Quayle, Michael J.,Timms, Peter L.,Whittell, George R.
, p. 4032 - 4037 (2007/10/03)
The reactions between B2F4 and the platinum and iridium complexes [Pt(PPh3)2(η-C2H4)], [Pt(dppb)(r)-C2H4)] [dppb = l,4-bis(diphenylphosphino)butane] and trans-[IrCl(CO)(PPh3)2] afforded the difluoroboryl complexes cis-[Pt(BF2)2(PPh3)2], cis-[Pt(BF2)2(dppb)] and fac-[Ir(BF2)3(CO)(PPh3)2] respectively all of which have been characterised by X-ray crystallography. The isoelectronic platinum dppb nitrito complex cw-[Pt(NO2)2(dppb)] has also been prepared and structurally characterised. The Royal Society of Chemistry 2000.
Reactions of (chloromethyl)platinum(II) derivatives with nucleophiles. Formation of (dimethylamino)carbene complexes using N,N,N′,N′-tetramethylmethanediamine as nucleophile and the X-ray crystal and molecular structures of cis-[(Ph3P)Pt(CH2NMe3)Cl2]
Ferguson, George,Li, Yiwei,McAlees, Alan J.,McCrindle, Robert,Xiang, Ke
, p. 2428 - 2439 (2008/10/08)
Reaction, in chloroform solution, of (COD)Pt(CH2Cl)Cl (5) with Me2NCH2NMe2 in the presence of 1 equiv (vs 5) of a monodentate ligand L (L = Ph3P, (p-MeOC6H4)3P, (p-FC6H4)3P, Et3P, Ph3As) gives the (dimethylamino)carbene complexes cis-[LPt(CHNMe2)Cl2] (1a-e) via the cyclic ylide intermediates [LPt(CH2NMe2CH2NMe2)Cl]Cl (2a-e). Major byproducts of the reaction are the (trimethylammonio)methyl ylide complexes cis-[LPt(CH2NMe3)Cl2] (11a-e). With L = Ph3As, carbene product 1e is accompanied by a second carbene complex, trans(As,CH2)-[(Ph3As)Pt(CHNMe2)(CH 2NHMe2)Cl]Cl (25). When the reaction with L = Ph3P is carried out in acetonitrile, the amide chelate [(Ph3P)Pt(CH2CH2CONMe2)Cl] (24) is formed in addition to 1a and 11a. A deuterium labeling experiment indicates that formation of 24 involves condensation of a CH2Cl (or derived) moiety with a molecule of solvent. The structures of complexes 11a and 24, and of the hexafluorophosphate analogue (26) of complex 25, have been confirmed by X-ray crystallographic analyses. Carbene complex 1a, along with other products, is also obtained upon reaction of 5 and Ph3P (1:1) with dimethylamine. Formation of 1a in this case can proceed via two pathways, one involving cyclic ylide species 2a as intermediate and the other the N-protonated (dimethylamino)methyl complex cis-[(Ph3P)Pt(CH2NHMe2)Cl2] (20). The mechanistic pathways involved in formation of carbene complexes 1a-e and 25, ylide complexes 2a-e and 11a-e, and (dimethylamino)methyl complex 20 are discussed. It is suggested that formation of the ylide complexes and 20 proceeds via initial attack of amine at platinum and that carbene formation proceeds via platinum(IV) carbene hydride intermediates.
Phosphine exchange reactions involving cis-[Pt(PPh3)2(Bcat)2] (cat = 1,2-O2C6H4) and the oxidative addition of 1,2-B2Cl2(NMe2)2 to Pt0
Curtis, David,Lesley, M.J. Gerald,Norman, Nicholas C.,Orpen, A. Guy,Starbuck, Jonathan
, p. 1687 - 1694 (2007/10/03)
The reaction between the platinum(II) bis(boryl) complex cis-[Pt(PPh3)2(Bcat)2] (cat = 1,2-O2C6H4) and the tertiary phosphines PMe3, PEt3, PMe2Ph, PMePh2 and dcpe [1,2-bis(dicyclohexylphosphino)ethane] and the phosphite P(OEt)3 afforded the new complexes cis-[Pt(PR3)2(Bcat)2] (PR3 = PMe3, PEt3, PMe2Ph or PMePh2), cis-[Pt(dcpe)-(Bcat)2] and cis-[Pt{P(OEt)3}2(Bcat)2]. With PCy3 the mixed phosphine species cis-[Pt(PCy3)(PPh3)(Bcat)2] is the major product and was characterised by X-ray crystallography. With P(OMe)3 reductive elimination of B2(cat)2 and the formation of platinum(0) products occurs exclusively whereas with dmpe [1,2-bis(dimethylphosphino)ethane] the only identifiable product is the platinum(ii) species [Pt(dmpe)2]Cl2. With dppm [bis(diphenylphosphino)methane] a reaction occurs to give a product assigned the structure cis-[Pt(dppm)(Bcat)2] or [Pt2(dppm)2(Bcat)4] but two binuclear products were isolated as minor products, namely [Pt2(PPh3)(μ-dppm)2(Bcat)(μ-Bcat)] and [Pt2(κ1-dppm)-(μ-dppm) 2(Bcat)(μ-Bcat)]. Both compounds were characterised by X-ray crystallography and shown to contain unusual semi-bridging Bcat groups. The reaction between [Pt(PPh3)2(η-C2H4)] and the diborane(4) compound 1,2-B2Cl2(NMe2)2 is also described which results in B-B bond oxidative addition yielding cis-[Pt(PPh3)2{BCl(NMe2)}2] and a complex to which this bis(boryl) subsequently rearranges, namely trans-[PtCl(PPh3)2{BCl(NMe2)}]. Both of these complexes were characterised by X-ray crystallography and have geometries typical of cis-bis(boryl) and trans-boryl chloride complexes respectively.
Synthesis of Δ2-1,3-oxazolines from cationic platinum(II) nitrile complexes. X-ray structure of trans-[Pt(CF3){N=C(Ph)OCH2CH2}(PPh 3)2]BF4·0.5H 2O·0.25MeOH
Michelin, Rino A.,Mozzon, Mirto,Berin, Paola,Bertani, Roberta,Benetollo, Franco,Bombieri, Gabriella,Angelici, Robert J.
, p. 1341 - 1350 (2008/10/08)
Cationic Pt(II) nitrile complexes of the type trans-[Pt(R′)(NCR)(PPh3)2]BF4 (R′ = H (1), CH3 (2), R = CH3; R′ = CF3, R = CH3 (3), CH3CH2 (4), CH3CH2CH2 (5), (CH3)2CH (6), (CH3)3C (7), C6H5 (8), p-CH3C6H4 (9), o-CH3C6H4 (10), p-OCH3C6H4 (11)) have been prepared by reaction of the corresponding halo complexes trans-[Pt(R′)X(PPh3)2] (X = Cl, Br) with AgBF4 in the presence of a 20-30-fold excess of RCN in CH2Cl2. The complexes 1-11 readily react in THF at 0°C or below with HOCH2CH2Cl/n-BuLi (n-BuLi:complex molar ratio 1:1) to give a mixture of products, including the oxazoline complexes trans-[Pt(R′){N=C(R)OCH2CH2}(PPh3) 2]BF4 (1a-11a), the chloro complexes trans-[Pt(Cl(R′)(PPh3)2, and free oxazoline N=C(R)OCH2CH2. For short reaction times (ca. 10-15 min) the oxazoline complexes 1a-11a could be isolated albeit in modest yield (26-49%) from the reaction mixtures and they could be separated from the corresponding chloro complexes (average yield ca. 35%) by taking advantage of the higher solubilty of the latter derivatives in benzene. For longer reaction times (>2 h), the trans-[PtCl(R′)(PPh3)2] species were the only isolated products. Compounds 1a-11a have been characterized by IR and multinuclear (1H, 19F, 31P{1H}, and 13C{1H}) NMR spectroscopies and also by an X-ray structural determination, which has been carried out for 3a. It crystallizes in the orthorhombic space group Pna21, with a = 19.130(4) A?, b = 15.936(3) A?, c = 16.312(3) A?, V = 4973(2) A?3, and Z = 4. The structure was refined to R = 0.056 (Rw = 0.065) for 2485 measured reflections with I ≥ 3σ(I). The 2-(phenyl)oxazoline ligand is almost planar and perpendicular to the mean coordination plane. A mechanism is proposed for the conversion of nitriles to 2-oxazolines in cationic Pt(II) complexes. The reactions of the isolated complexes trans-[Pt(CF3){N=C(R)OCH2CH2}(PPh 3)2]BF4 (3a-11a) with excess chloride ions gave trans-[Pt(CF3)Cl(PPh3)2] and the corresponding free oxazolines, which were characterized by IR, 1H NMR, and GC/MS techniques. Attempts to generate catalytically 2-(methyl)oxazoline have been performed using the trans-[PtX(R)(PR3)2]/CH3CN/OCH 2CH2 system (PR3 = PEt3, PMe2Ph; R = H, CH3, CF3; X = Br, I). No oxazoline formation was observed between 50 and 75°C and 36 and 160 h; however, addition of LiBr and OCH2CH2 to trans-[PtBr(CH3)(PEt3)2] and trans-[PtBr(CF3)(PMe2Ph)2] (salt:complex (1.5-3):1 molar ratio) led to the formation of 2-(methyl)oxazoline, albeit not catalytically.
