A. S. Batsanov

Reaction of (η-C5H5)(CO)2Mn(η2-HCCCO2Me) with phosphines. Crystal and molecular structure of (η-C5H5(CO)2Mn−C(CO2Me)CHP+Ph3

Abstract Reaction of Cp(CO) 2 Mn(η 2 -HCCCO 2 Me) (I) with PPh 3 or (Ph 2 PCH 2 ) 2 gives rise to π—σ-rearrangement of the methylpropiolate ligand in I, yielding the phosphonium ylide complexes Cp(CO) 2 Mn − C(CO 2 Me)CHP + Ph 2 R, where R = Ph or CH 2 CH 2 PPh 2 . The structure of II was established by X-ray crystallography.

Cyclopentadienyldicarbonylmanganese phosphonium ylide complexes. X-ray crystal and molecular structure of (η-C5H5)(CO)2Mn−C(P+Ph3)CCPh2·CH2Cl2

Abstract Unsaturated carbene complexes of manganese, Cp(CO)2MnCCHR and Cp(CO)2MnCCCR′2 (Cp = η-C5H5, R = Ph, CO2Me, C(t-Bu)2OH; R′=t-Bu, Ph), add phosphines to the α-carbon atom of a cumulidene ligand to yield the phosphonium ylide complex Cp(CO)2Mn− C(P+Ph2R″)CHR (R″ = Ph, Me) or Cp(CO)2Mn− C(P+Ph3)CCR′2. The latter complex (with R′ = Ph) was studied by X-ray crystallography as a 1:1 solvate with CH2Cl2.

Protonation of allenylidene- and vinylidene-manganese complexes. Crystal and molecular structure of [Cp(CO)2MnCCHCPh2]+ BF4t

Abstract The cyclopentadienylmanganese carbonyl complexes with terminal allenylidene ligands, Cp(CO)2MnCCCR2 (R = But, Ph), are protonated by HX acids (X = Cl, BF4, CF3COO) yielding cationic vinylcarbyne complexes of the type [Cp(CO)2MnCCHCR2]+X−. One of these, with R = Ph, X = BF4, was characterized by X-ray crystallography. The MnC bond of 1.665 A in it is the shortest one known to date. The binuclear μ-vinylidene complexes, [Cp(CO)2,Mn]2CCHR′ (R′ = Ph, COOMe) are also protonated at the β-carbon atom of the vinylidene ligand.

Synthesis and characterization of bis-(diphenylphosphinoethane) -substituted hexarhodium clusters: Rh6(CO)14(μ2,η2 -Ph2P(CH2)2PPh2), Rh6(CO)152 (μ2,η1 : η1-Ph2P(CH2)2 PPh2) and Rh6(CO)15(η1-Ph2 P(CH2)2P(O)Ph2). X-Ray crystal structures of Rh6(CO)15PPh3 and Rh6(CO)14 (μ2,η2-Ph2P(CH2)2PPh2) clusters

Abstract Two major products of the photoreaction between Rh6(CO)16 and bis-(diphenylphosphinoethane) (dppe) were isolated and characterized as Rh6(CO)14(μ2, η2 -Ph2P(CH2)2 PPh2) with μ2-bridging bidentate dppe and Rh6(CO)15(η1-Ph2P(CH2)2P (O)Ph2) where one P atom of dppe is terminally coordinated, the other being oxidized and thus non-coordinated. Substitution of the labile acetonitrile ligand in Rh6(CO)15,NCMe by dppe yields Rh6(CO)15 2(μ2,η1:η1-Ph2P(CH2)2PPh2) with dppe bridging two Rh6 cores. The structures of Rh6(CO)14(μ2,η2 -Ph2P(CH2)2PPh2) and Rh6(CO)15PPh 3 have been determined by single-crystal X-ray diffraction studies. Solution structures of Rh6(CO)14(μ2,η2-Ph2P(CH2)2PPh 2), Rh6(CO)15PPh3, Rh6(CO)15(η1- Ph2P(CH2)2 P(O)Ph2) and Rh6(CO)152(μ2,η1:η1-Ph2P(CH2) 2PPh2) have been established by IR, and 13C and 31P NMR spectroscopy.

Preparation of heterometallic complexes with chelating μ2-carbomethoxyvinylidene ligands. X-ray crystal structures of Cp(OC)2 MnW(CO)4(μ-CCHCOOMe) and [Cp(OC)2Mn(μ2-CCHCOOMe)]2Mo(CO)2 (Cp = η5-C5H5)

Abstract Cp(OC) 2 MnCCHCO 2 Me and Cp(OC) 2 Mn(η 2 -HCCCO 2 Me) react with M(CO),(THF) (M = Mo, W) yielding the heterometallic complexes Cp(OC) 2 Mn M(CO) 4 (μ-CCHCO OMe) (VIa: M = W, VIb: M = Mo) and [Cp(OC) 2 Mn(μ 2 -CCHC OO Me)] 2 M o(CO) 2 (VII). VIa and VIb have MnW and MnMo bonds and VII has two MnMo bonds bridged by the carbomethoxyvinylidene ligand, chelating Mo or W by carbonyl oxygen. VIa and VII have been characterized by an X-ray diffraction study.

Reactions and Synthesis, Wiley-Interscience, New York The reaction with amines of the adduct formed between (cinnamaldehyde)tetracarbonyliron π-complex and bf3. molecular structure of the formed σ-N-Tetra carbonyliron complexes of cinnamaldehyde imines

Abstract The adduct formed on reaction of boron trifluoride etherate with (π-PhCHCHCHO)Fe(CO) 4 by addition of BF 3 to the oxygen atom of the aldehyde group, reacts with primary amines to give σ- N -tetracarbonyliron derivatives of cinnamaldehyde imines via (enimonium)tetracarbonyliron π-complexes. The structure of the former complexes is established by X-ray analysis and the effect of steric factors on π → σ( N ) rearrangernent is discussed.

Synthesis and structure of the 1,1′-trimethylenebenzene- cyclopentadienyliron cation.

Abstract 1,1′-Bis(3-phenylpropyl)ferrocene reacts with AlCl3/Al inheptane to yield 1,1′trimethylenebenzenecyclopentadienyliron hexafluorophosphate (I). The structure of complex I was established by X-ray analysis.

Iron carbonyl complexes containing an azomethyne moiety: I. Synthesis and x-ray structure of a novel σ,π-arene-bridged complex, μ-(o-C6H4CH2NC6H5)Fe3(CO)8

Abstract N -(Benzylidene)aniline (BZA) reacts with Fe 3 (CO) 12 yielding μ-( o -C 6 H 4 CH 2 NC 6 H 5 )Fe 2 (CO) 6 (I), μ-( o -C 6 H 4 CH 2 NC 6 H 5 )Fe 3 (CO) 8 (II) and various products from the reduction and carbonylation of BZA and its fragments. II was characterized by X-ray crystallography and proved to be the first complex prepared with a σ,π(η 1 ,η 6 )-bridging arene ligand.

Unusual infinite-chain anion [Cu2I−3-]∞ in the structure of its thiopyrilium salt

Abstract The crystal structure of [C23H17S]+[Cu2I3]− (C23H17S = 2,4,6-triphenylthiopyrilium) has been determined at -120 °C and refined by least-squares to R = 0.033 using 2861 intensities collected by the counter method. Black crystals obtained are hexagonal, a = 13.856(5), c = 20.778(4) A, space group P61, Z = 6. The structure contains infinite anions [Cu2I−3]∞, the chains of I4 tetrahedra being centered by Cu atoms and joined via their faces and edges. The shortest Cu⋯Cu distances where 2.479 and 2.634 A. The discrete [C23H17S]+ cations are disordered. Similar complexes with other heterocyclic cations have been prepared.

Interaction of vinylgermanes with iron carbonyls. X-ray crystal structure of the Ge[Fe(CO)4]4 complex

Abstract The reaction between vinylgermanes and iron carbonyls yields, besides π-olefin complexes, the cluster compound Ge[Fe(CO) 4 ] 4 (I), characterized here by X-ray crystallography. The presence of an unsaturated substituent at the Ge atom plays an important role in the formation of I.