Dmitry A. Loginov

Iron- and Ruthenium-Containing Triple-Decker Complexes with a Central Pentaphospholyl Ligand − X-ray Structures of [(η-C5H5)Fe(μ-η:η-P5)Ru(η-C5Me5)]PF6 and [(η-C5Me5)Ru(μ-η:η-P5)Ru(η-C5Me5)]PF6

Triple-decker cationic complexes with a central pentaphospholyl (pentaphosphacyclopentadienyl) ligand [Cp*M(μ-η:η-P5)M′(η-C5R5)]+ (3b: M = M′ = Fe, R = Me; 4a: M = Ru, M′ = Fe, R = H; 4b: M = Fe, M′ = Ru, R = H; 4c: M = Fe, M′ = Ru, R = Me; 5a: M = M′ = Ru, R = H; 5b: M = M′ = Ru, R = Me) were synthesized by exploitation of the stacking reactions of pentaphosphametallocenes Cp*M(η-P5) (1: M = Fe; 2: M = Ru) with half-sandwich fragments [(η-C5R5)M′]+. They were isolated as salts with BF4− or PF6− anions, and the structures of 4aPF6 and 5bPF6 were determined by X-ray diffraction. Triple-decker complexes with a central pentaphospholyl ligand are less reactive in nucleophilic degradation reactions than analogous complexes with C4Me4P and Cp* ligands in the bridging position. Only 4a and the previously known analogue 3a (M = M′ = Fe, R = H), containing the CpFe fragment, are nucleophilically destroyed by MeCN and NaI. The electrochemical properties of 2, 3a, 3b, 4a−c, 5a and 5b and the related cobalt-containing complexes [(η-C4Me4)Co(μ-η:η-P5)MCp*]+ (6: M = Fe; 7: M = Ru) were investigated. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Remarkable Structural and Electronic Features of the Complex Formed by Trimeric Copper Pyrazolate with Pentaphosphaferrocene

According to spectroscopic (NMR, IR, UV/Vis) study, the interaction of pentaphosphaferrocene [Cp*Fe(η(5) -P5 )] with trimeric copper pyrazolate [(Cu{3,5-(CF3 )2 Pz})3 ] yields a new compound that is astonishingly stable in solution. Single-crystal X-ray analysis reveals unprecedented structural changes in the interacting molecules and the unique type of coordination [Cp*Fe(μ3 -η(5) :η(2) ,η(2) -P5 ){Cu(3,5-(CF3 )2 Pz)}3 ]. As a result of the 90° macrocycle folding, the copper atoms are able to behave both as a Lewis acid and as a Lewis base in the interaction with the cyclo-P5 ligand.

Synthesis of triple-decker iron and cobalt complexes with a central tetramethylphospholyl ligand

Abstract30-Electron triple-decker complexes [(η-C5H5)Fe(μ-η:η-C4Me4P)Fe(η-C5Me5)]PF6 and [(η-C4Me4)Co(μ-η:η-C4Me4P)Fe(η-C5Me5)]PF6 with a central tetramethylphospholyl ligand were synthesized by stacking reactions of cationic fragments [(η-C5H5)Fe]+ and [(η-C4Me4)Co]+ with nonamethylphosphaferrocene (η-C4Me4P)Fe(η-C5Me5).

Iron and ruthenium triple-decker complexes with a central pentaphospholyl ligand

Thirty-electron triple-decker complexes with a central pentaphospholyl ligand [(η-C5Me5)Fe(μ-η:η-P5)M(η-C5R5)]BF4 (M=Fe, R=Me or M=Ru, R=H, Me) were synthesized by a stacking reaction of cationic 12-electron fragments [(η-C5R5)M]+ with (η-C5Me5)Fe(η-P5).

(Indenyl)iridacarborane (η5-indenyl)Ir(η-7,8-C2B9H11): synthesis, structure, and bonding

A reaction of iodide [(η5-indenyl)IrI2]n (1) with thallium dicarbollide Tl[Tl(η-7,8-C2B9H11)] leads to (indenyl)iridacarborane (η5-indenyl)Ir(η-7,8-C2B9H11) (2) in 32% yield. The X-ray diffraction study showed that in the structure of 2, the five-membered rings C5 and C2B3 have a cisoid conformation, in which the bridgehead carbon atoms of the indenyl ligand are arranged opposite to the carborane cage carbon atoms. The DFT calculations showed that the Ir—indenyl bond in compound 2 is weaker than the Ir—Cp bond in the complex (η-7,8-C2B9H11)IrCp.

Synthesis of dicationic triple-decker complexes with a central B-cyclohexyl-substituted borole ligand

Stacking reactions of the dicationic fragments [LM]2+ (LM = (η-C6H6)Ru, (η-C6H3Me3)Ru, or (η-C5Me5)Rh) with the complex (η-C5H5)Co(η-C4H4BCy) (Cy = cyclo-C6H11) afforded new dicationic 30-electron triple-decker complexes [(η-C5H5)Co(μ-η:η-C4H4BCy)ML](BF4)2 containing a cyclohexyl-substituted borole ligand in the central position.

CCDC 1544890: Experimental Crystal Structure Determination

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CCDC 1544888: Experimental Crystal Structure Determination

Related Article: Alexander P. Molotkov, Mikhail M. Vinogradov, Alexey P. Moskovets, Olga Chusova, Sergey V. Timofeev, Vasilii A. Fastovskiy, Yulia V. Nelyubina, Alexander A. Pavlov, Denis A. Chusov, Dmitry A. Loginov|2017|Eur.J.Inorg.Chem.||4635|doi:10.1002/ejic.201700498

CCDC 1544887: Experimental Crystal Structure Determination

Related Article: Alexander P. Molotkov, Mikhail M. Vinogradov, Alexey P. Moskovets, Olga Chusova, Sergey V. Timofeev, Vasilii A. Fastovskiy, Yulia V. Nelyubina, Alexander A. Pavlov, Denis A. Chusov, Dmitry A. Loginov|2017|Eur.J.Inorg.Chem.||4635|doi:10.1002/ejic.201700498