Telomerization of formamide with butadiene,catalyzed by palladium complexes

Conclusions It was shown that the N-2,7- and N-1,7-octadienylformamides can be obtained by the telomerization of formamide with butadiene using the four-component catalyst Pd²⁺-Ph₃P-AlEt₃-CF₃CO₂H.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khlmicheskaya, No. 3, pp. 703–704, March, 1984.     

Telomerization of alkane- and arenesulfonamides with butadiene catalyzed by palladium complexes

Conclusions The catalyzed (by palladium complexes) telomerization of butadiene with butane- and p-toluenesulfonamides, which leads to difficult-to-obtain N-substituted unsaturated sulfonamides in high yields, was realized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 372–376, February, 1985.     

Dioxygen activation by diiminodipyrromethane complexes of Ni, Pd, and Pt

Diiminodipyrromethane complexes of Ni, Pd, and Pt are able to activate O2, resulting in a metal-dependent autoxidation of the ligand.     

Telomerization of allene with water catalyzed by palladium complexes

Conclusions The telomerization of allene with water catalyzed by palladium complexes leads to the preparation of 3-methyl-2-methylene-3-buten-1-ol and 2,3,6,7-tetramethylene-1-octanol in high yields.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2624–2626, November, 1985.     

Ni, Pd, Pt, and Ru complexes of phosphine-borate ligands

The species Cy(2)PHC(6)F(4)BF(C(6)F(5))(2) reacts with Pt(PPh(3))(4) to yield the new product cis-(PPh(3))(2)PtH(Cy(2)PC(6)F(4)BF(C(6)F(5))(2)) 1 via oxidative addition of the P-H bond of the phosphonium borate to Pt(0). The corresponding reaction with Pd(PPh(3))(4) affords the Pd analogue of 1, namely, cis-(PPh(3))(2)PdH(Cy(2)PC(6)F(4)BF(C(6)F(5))(2)) 3; while modification of the phosphonium borate gave the salt [(PPh(3))(3)PtH][(tBu(2)PC(6)F(4)BF(C(6)F(5))(2))] 2. Alternatively initial deprotonation of the phosphonium borate gave [tBu(3)PH][Cy(2)PC(6)F(4)BF(C(6)F(5))(2)] 4, [SIMesH][Cy(2)PC(6)F(4)BF(C(6)F(5))(2)] 5 which reacted with NiCl(2)(DME) yielding [BaseH](2)[trans-Cl(2)Ni(Cy(2)PC(6)F(4)BF(C(6)F(5))(2))(2)] (Base = tBu(3)P 6, SIMes 7) or with PdCl(2)(PhCN)(2) to give [BaseH](2)[trans-Cl(2)Pd(Cy(2)PC(6)F(4)BF(C(6)F(5))(2))(2)] (Base = tBu(3)P 8, SIMes 9). While [C(10)H(6)N(2)(Me)(4)H][tBu(2)PC(6)F(4)BF(C(6)F(5))(2)] 10 was also prepared. A third strategy for formation of a metal complex of anionic phosphine-borate derivatives was demonstrated in the reaction of (COD)PtMe(2) with the neutral phosphine-borane Mes(2)PC(6)F(4)B(C(6)F(5))(2) affording (COD)PtMe(Mes(2)PC(6)F(4)BMe(C(6)F(5))(2)) 11. Extension of this reactivity to tBu(2)PH(CH(2))(4)OB(C(6)F(5))(3)) was demonstrated in the reaction with Pt(PPh(3))(4) which yielded cis-(PPh(3))(2)PtH(tBu(2)P(CH(2))(4)OB(C(6)F(5))(3)) 12, while the reaction of [SIMesH][tBu(2)P(CH(2))(4)OB(C(6)F(5))(3)] 13 with NiCl(2)(DME) and PdCl(2)(PhCN)(2) afforded the complexes [SIMesH](2)[trans-Cl(2)Ni(tBu(2)PC(4)H(8)OB(C(6)F(5))(3))(2)] 14 and [SIMesH](2)[trans-PdCl(2)(tBu(2)P(CH(2))(4)OB(C(6)F(5))(3))(2)] 15, respectively, analogous to those prepared with 4 and 5. Finally, the reaction of 7 and 13with [(p-cymene)RuCl(2)](2) proceeds to give the new orange products [SIMesH][(p-cymene)RuCl(2)(Cy(2)PC(6)F(4)BF(C(6)F(5))(2))] 16 and [SIMesH][(p-cymene)RuCl(2)(tBu(2)P(CH(2))(4)OB(C(6)F(5))(3))] 17, respectively. Crystal structures of 1, 6, 10, 11, 12, and 16 are reported.     

Cyclopentadienyl derivatives of magnesium and sodium in cross-combination reaction with allyl compounds catalyzed by Pd complexes

Conclusions An effective method was developed for synthesizing allylcyclopentadienes by cross-combination of cyclopentadienyl derivatives of magnesium and sodium with O-, N-, and C-containing allyl compounds in the presence of palladium complexes. The substituted cyclopentadienes obtained comprise equilibrium mixtures of isomers, containing 1- and 2-allylcyclopentadienes in a 1:1 ratio.Translated from Izvestiya AkademiiNauk SSSR, Seriya Khimicheskaya,. No. 11, pp. 2562–2566, November, 1985.     

Telomerization of conjugated dienes and trienes with pyrazolines catalyzed by palladium complexes

Conclusions The telomerization of pyrazolines with 1,3-dienes and trienes in the presence of homogeneous Pd catalysts results in the synthesis of the corresponding N-2,7-octadienyl derivatives of heterocyclic amines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 652–655, March, 1980.     

Double carbonylation of aryl iodides with diethylamine catalyzed by dinuclear palladium complexes

Dinuclear palladium complexes bridged by a novel PNNP ligand, N,N′-bis[(2-diphenylphosphino)phenylformamidinate (dpfam), were found to be very efficient and selective catalysts for the double carbonylation of iodobenzene with diethylamine using K₃PO₄ as base and 1,4-dioxane as solvent with a TON up to 10⁵ and selectivity of 96%.     

Cross-coupling and dehalogenation reactions catalyzed by (N-heterocyclic carbene)Pd(allyl)Cl complexes

A series of well-defined, air- and moisture-stable (NHC)Pd(allyl)Cl (NHC = N-heterocyclic carbene) complexes has been used in several catalytic reactions: Suzuki-Miyaura cross-coupling, catalytic dehalogenation of aryl halides, and aryl amination. The scope of the three processes using various substrates was examined. A general system involving the use of (IPr)Pd(allyl)Cl as catalyst and NaO(t)Bu as base has proven to be highly active for the Suzuki-Miyaura cross-coupling of activated and unactivated aryl chlorides and bromides, for the catalytic dehalogenation of aryl chlorides, and for the catalytic aryl amination of aryl triflates. All reactions proceed in short reaction times and at mild temperatures. The system has also proven to be compatible with the microwave-assisted Suzuki-Miyaura cross-coupling and catalytic dehalogenation processes, affording yields similar to those of the conventionally heated analogous reactions.     

Controlled alkylation of hydroxylamines with butadiene catalyzed by palladium complexes

Conclusions A method has been developed for the synthesis of N- and O-2,7-octadienyl derivatives of hydroxylamines by reaction of butadiene with hydroxylamine and its alkyl- and aryl-substituted analogs in the presence of the catalyst Pd(acac)₂-Ph₃P-AlEt₃-CF₃CO₂H in N-methylpyrrolidone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2254–2256, October, 1986.     

Telluro- and seleno-bridged TiIV-MII (M = Ni,Pd, Pt) heterobimetallic complexes

Summary Heterobimetallic complexes of the types [Cp₂Ti(-EAr)₂-M(dppe)] (ClO₄)₂ [(1)–(4); M, E = Ni, Te (1); Ni, Se (2); Pt, Te (3); Pt, Se (4); Ar = Ph (a), C₆H₄-4-Me (b), C₆H₄-4-OMe (c), C₆H₄-4-OEt (d)] and [Cp₂Ti(-TeAr)₂-MCl ₂] [M = Pd (5), Pt (6)] were obtained by the reactions of Cp₂Ti(EAr)₂ with M(dppe)(ClO₄)₂ and M(PhCN)₂Cl₂, respectively. While (1), (5) and (6) are stable in the solid state as well as in solution, (2)–(4) undergo dissociation to M(dppe)(EAr)₂ and Cp₂Ti(ClO₄)₂ in solution, as shown by multinuclear (³¹P{¹H},¹⁹⁵Pt{¹H}, ¹²⁵Te{¹H}) n.m.r. studies. The reaction of Cp₂Ti(SeAr)₂ with M(PhCN)₂Cl₂, however, leads to the formation of Cp₂TiCl₂ and a polymeric material [M(SeAr)₂] _n .     

Geometrical characteristics of four-coordinate complexes of Ni,Pd, and Pt containing triphenylphosphine as ligand

A statistical analysis based on crystal structure results of 4-coordinated complexes of Ni, Pd, and Pt containing triphenylphosphine as ligand has been performed using the Cambridge Structural Data Base. Distorted square-planar coordination appears as the most probable one presented by these metals.

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Geometrische Charakteristika von vier-koordinierten Komplexen des Ni, Pd und Pt mit Triphenylphosphin als Ligand

Zusammenfassung Es wurde unter Verwendung der Cambridge Strukturdatenbank eine statistische Analyse von Resultaten an vier-koordinierten Komplexen des Ni, Pd und Pt mit Triphenylphosphin-Ligand durchgeführt. Dabei ergab sich eine verzerrte quadratisch-planare Koordination als die am meisten wahrscheinliche Geometrie.