Facile method for the synthesis of ruthenacarboranes, diamagnetic 3,3-[Ph2P(CH2)nPPh2]-3-H-3-Cl-closo-3,1,2-RuC2B9H11 (n = 3 or 4) and paramagnetic 3,3-[Ph2P(CH2)nPPh2]-3-Cl-closo-3,1,2-RuC2B9H11 (n = 2 or 3), as efficient initiators of controlled radical polymerization of vinyl monomers

A facile preparative procedure was developed for the synthesis of 17-and 18-electron closo-(diphosphine)ruthenacarborane complexes. This method is based on the replacement of PPh₃ ligands with bis(diphenylphosphino)alkanes Ph₂P(CH₂)_nPPh₂ (n = 2—4) in ruthenacarborane 3,3-(PPh₃)₂-3-Cl-3-H-closo-3,1,2-RuC₂B₉H₁₁. The resulting complexes exhibit high activity in controlled radical polymerization of vinyl monomers.     

Synthesis and the structure of the triphenylphosphine complex of o-nickelacarborane, 3,3-(PPh3)2-3,1,2-NiC2B9H11

The reaction of bis(o-dicarbollyl)nickel(iv) with PPh₃ in EtOH gave rise to the complex 3,3-(PPh₃)₂-3,1,2-NiC₂B₉H₁₁ (2) whose structure was established by X-ray diffraction analysis.     

Synthesis of 9-C6H5-3-(π-C5H5)-3,1,2-CoC2B9H10 by cross-coupling reaction of 9-I-3-(π-C5H5)-3,1,2-CoC2B9H10 with C6H5ZnCl catalyzed by palladium complexes

The cross-coupling reaction of 9-I-3-(π-C₅H₅)-3,1,2-CoC₂B₉H₁₀ with organozinc compounds catalyzed by palladium complexes was used to synthesize the first representative ofB-phenyl-substituted carboranes, 9-C₆H₅-3-(π-C₅H₅)-3,1,2-CoC₂B₉H₁₀. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No: 6, pp. 1253–1254, June, 1998.     

Sterically-induced low temperatur polyhedral rearrangements of carbaplatinaboranes: Synthesis and crystal structures of 1-Ph-3,3-(PMe2Ph)2-3,1,2-PtC2B9H10, 1-Ph-3,3-(PMe2Ph)2-3,1,11-PtC2B9H10, 11-Ph-3,3-(PMe2Ph)2-3,1,11-PtC2B9H10 and 1,11-Ph2-3,3-(PMe2Ph)2-3,1,11-PtC2B9H9

Reaction of cis-Pt(PMe₂Ph)₂Cl₂ with Tl₂[7-Ph-7,8-nido-C₂B₉H₁₀] affords 1-Ph-3,3-(PMe₂Ph)₂-3,1,2-PtC₂B₉H₁₀, mild thermolysis (55°C) of which yields 1-Ph-3,3-(PMe₂Ph)₂-3,1,11-PtC₂B₉H₁₀ and 11-Ph-3,3-(PMe₂Ph)₂-3,1,11-PtC₂B₉H₁₀. Both of the latter compounds are produced by the microwave irradiation of a mixture of cis-Pt(PMe₂Ph)₂Cl₂ and [HNMe₃][7-Ph-7,8-nido-C₂B₉H₁₁]. When cis-Pt(PMe₂Ph)₂Cl₂ is allowed to react with Tl₂[7,8-Ph₂-7,8-nido-C₂B₉H₉] at room temperature the only isolable species is 1,11-Ph₂-3,3-(PMe₂Ph)₂-3,1,11-PtC₂B₉H₉. The generation of rearranged products with 3,1,11-PtC₂B₉ architectures is inconsistent with a diamond-square-diamond mechanism for the isomerisation of icosahedral heteroboranes.     

The relationship between the molecular structure of [3,3-(PMe2Ph)2-closo-3,1,2-PtC2B9H11] and the mechanism of the fluxional behaviour of M(PR3)2-units in closo-twelve-atom metallaheteroboranes

The upper limit of the free energy of the barrier to rotation of the platinum bis-phosphine unit in [3,3-(PMe₂Ph)₂-closo-3,1,2-PtC₂B₉H₁₁] 1 is 30< kJ mol⁻¹ in dichloromethane solution. This relatively low value is similar in magnitude to crystal-packing forces, and compound 1 crystallises from CH₂Cl₂-hexane solution as a 1 : 1 mixture of two different conformers with significantly different platinum-to-C₂B₃ bonding. These observations lead to the proposal of a general mechanism for the mutual rotation of {M(PR₃)₂} units above C₂B₉H₁₁.     

New 11-vertex osmacarborane 1,1-(PPh3)2-1-H-3-O(CH2)4-isonido-1,2,4-OsC2B8H9

Russian Chemical Bulletin - Hydride-containing 1,1-(PPh3)2-1-H-3-O(CH2)4-isonido-1,2,4-OsC2B8H9 osmacarborane bearing a charge-compensated ligand was synthesized via a reaction of the deprotonated...     

(C60)2Ru2Cl4[Ph2P(CH2)4PPh2]配合物的合成

在氮气氛中采用配体取代法合成了C60以σ-π配位方式与Ru形成的稳定η2型富勒烯双核钌金属配合物(C60)2Ru2Cl4[Ph2P(CH2)4PPh2],其结构经UV,IR,XPS,XRD和元素分析表征.     

Synthesis of monohalogeno derivatives of closo-[B9H9]2-. Crystal structures of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I)

By reaction of Na2[B9H9] with the appropriate N-halogenosuccinimide, the monohalogenated anion [1-XB9H8]2- (X = Cl, Br, or I) is formed. The X-ray diffraction analyses performed on single crystals of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I) reveal that the tricapped trigonal prismatic geometry of the cluster is retained after substitution in the 1-position. Crystallographic data are as follows for (Ph4P)2[1-XB9H8].CH3CN. X = Cl, Br: monoclinic, space group P2(1), a = 10.7 A, b = 32.9 A, c = 13.8 A, beta = 96 degrees, Z = 4, R1 = 0.038 and R1 = 0.036, respectively. X = I: monoclinic, space group P2(1)/n, a = 10.5 A, b = 13.6 A, c = 33.4 A, beta = 94 degrees, Z = 4, R1 = 0.094. The compounds have been characterized by vibrational and 11B NMR spectroscopy as well.     

Synthesis and structure of novel [Ph(RO)PSe2]- complexes

Reaction of (PhPSe2)2(Woollins reagent) with NaOR (R = Me, Et, (i)Pr) gives the non-symmetric phosphonodiselenoato anions [Ph(RO)PSe2]- which can be complexed to a range of metals. The nickel complex Ni[Ph(MeO)PSe2]2 adopts a square-planar ML2 structure while the cadmium complex Cd[Ph(MeO)PSe2]2 displays a dimeric M2L4 structure. Two different lead complexes are observed, one consisting of PbL2 units joined by Pb...Se interactions to form distinct dimeric pairs. The other displays a novel dimeric structure built around a central four-membered Pb2Se2 ring. All new compounds have been characterised spectroscopically (31P, 1H, 13C NMR, IR, mass spectroscopy), by elemental analysis and five demonstrative X-ray structures are reported.     

Neue Silber‐Tellurid Cluster stabilisiert mit zweizähnigen Phosphanen: Synthese und Struktur von {[Ag5(TePh)6(Ph2P(CH2)2PPh3)](Ph2P(CH2)2PPh2)}∞, [Ag18Te(TePh)15(Ph2P(CH2)3PPh2)3Cl] und [Ag38Te13(TetBu)12(Ph2P(CH2)2PPh2)3]

Novel Silver‐Telluride Clusters Stabilised with Bidentate Phosphine Ligands: Synthesis and Structure of {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞, [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl], and [Ag₃₈Te₁₃(Te t Bu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] Bidentate phosphine ligands have been found effective to stabilise polynuclear cores containing silver and chalcogenide ligands. They can act as intra and intermolecular bridges between the silver centres. The clusters {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞ ( 1 ), [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl] ( 2 ), and [Ag₃₈Te₁₃(TetBu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] ( 3 ) have been prepared and their molecular structure determined. Compound 2 and 3 are molecular structures with separated cluster cores while 1 forms a polymeric chain bridged by phosphine ligands. ( 1 : space group P2₁/c (No. 14), Z = 4, a = 3518,1(7) pm, b = 2260,6(5) pm, c = 3522,1(7) pm, β = 119,19(3)°; 2 : space group R3 (No. 148), Z = 6, a = b = 3059,4(4) pm, c = 5278,8(9) pm; 3: space group Pccn (No. 56), Z = 4, a = 3613,0(9) pm, b = 3608,6(7) pm, c = 2153,5(8) pm)     

The cis-Re(Ph2PCH2CH2PPh2)2)+ metal centre. Synthesis and molecular structure of the dinitrile complex cis-[Re(NCC6H4Me-4 2(Ph 2 PCH 2 CH 2 PPh 2 2 ][BF4]

Reaction of NCC₆H₄X-4 (X  Me, OMe, or Cl) with trans-[ReCl(N₂)(dppe)₂] (dppe  Ph₂PCH₂CH₂PPh₂), at room temperature, in the presence of Tl[BF₄], gives the corresponding complexes cis-[Re(NCC₆H₄X-4)₂(dppe)₂][BF₄] (1); the crystal structure of 1 (X  Me) has been determined by single crystal X-ray diffraction analysis.