1,2-Bis(diphenylphosphino)ethane-containing commo-ferracarboranes of unusual structure

commo-Ferracarboranes [InlineEquation not available: see fulltext.] and [8-{(nido-7″,8″-C2B9H11-9″(11″)-)Ph2PCH2CH2PPh2}-commo-3,3′-Fe-{1,2-C2H9B10}{1′2′-C2B9H11}] were prepared as minor products in the metallation reaction of [K]+[nido-7,8-C2B9H12]− with the 14-electron iron complex [Ph2P(CH2)2PPh2]FeCl2. The structures of the complexes were determined by single-crystal X-ray diffraction. © 2019, Springer Science+Business Media, Inc

Synthesis and molecular structure of a manganese tricarbonyl complex based on 5,6-nido-C2B8H12 carborane

The anionic manganese tricarbonyl complex [1,1,1-(CO)3-isonido-1,2,4-MnC2B8H10]–was synthesized in the form of PPN and tmdaH salts (PPN is bis(triphenylphosphine)iminium, tmda is N,N,N’,N’-tetramethyl-1,8-diaminonaphthalene) by the reaction of the deprotonated form of the medium-size non-icosahedral carborane 5,6-nido-C2B8H12 with Mn(CO)5Br. The structure of the complex [tmdaH][1,1,1-(CO)3-isonido-1,2,4-MnC2B8H10] was deter-mined by X-ray diffraction. © 2017, Springer Science+Business Media, LLC, part of Springer Nature

Adducts of Mn and Re vinylidenes with P-OR nucleophiles: Hydrolysis rather than the intramolecular Michaelis-Arbuzov rearrangement

The reactions of vinylidene complexes S(cyrillic)r(cyrillic)(CO)2Mn = C=C(H)Ph (Mn1) and Cp(CO)2Re = C=C(H)Ph (Re1) with P-OR nucleophiles P(OR)R'R" (OR = R' = R" = OMe, OEt, OPri, OPh; OR = OEt, R' = R" = Ph; OR = R' = OEt, R" = Ph) proceed as nucleophilic addition to the Cα vinylidene atom to initially afford zwitter-ionic complexes Z-S(cyrillic)r(cyrillic)(CO)2M--C[+P(OR)R'R"] = C(H)Ph which were identified by spectroscopic methods and, in some cases, their molecular structures were confirmed by X-ray diffraction. These adducts are extremely sensitive to water and hydrolyzed by water traces to afford the corresponding η 2-phosphorylalkene complexes Cp(CO)2M(η2-E-HC[P(O)R'R"] = C(H)Ph). The isotopic label experiments with D2O and H2 18O showed the hydrolysis to proceed with the phosphorus-oxygen bond cleavage and binding of the water hydrogen to the carbon atom bearing the > P=O group. © 2017

Synthesis and molecular structure of a manganese tricarbonyl complex based on 5,6-nido-C2B8H12 carborane

The anionic manganese tricarbonyl complex [1,1,1-(CO)3-isonido-1,2,4-MnC2B8H10]–was synthesized in the form of PPN and tmdaH salts (PPN is bis(triphenylphosphine)iminium, tmda is N,N,N’,N’-tetramethyl-1,8-diaminonaphthalene) by the reaction of the deprotonated form of the medium-size non-icosahedral carborane 5,6-nido-C2B8H12 with Mn(CO)5Br. The structure of the complex [tmdaH][1,1,1-(CO)3-isonido-1,2,4-MnC2B8H10] was deter-mined by X-ray diffraction. © 2017, Springer Science+Business Media, LLC, part of Springer Nature

Supramolecular design of the trinuclear silver(I) and copper(I) metal pyrazolates complexes with ruthenium sandwich compounds via intermolecular metal−π interactions

The interaction of copper(I) and silver(I) macrocyclic pyrazolates with aromatic ligands of ruthenium sandwiches (Cp*RuInd, CpRuInd, and Ind2Ru) in solution is shown for the first time. The similar mode of coordination of macrocycles to the C6 fragment of indenyl ligand was found both in the solution and in the solid state. Complexation of macrocycles with the nonencumbered sandwiches (CpRuInd, Ind2Ru) leads to the formation of infinite stacks via alternating molecules of macrocycles and sandwich compounds as one-dimensional coordination polymers with a regular structure. Coordination mode of the indenyl ligand is independent of the second part of the ruthenium sandwich as well as of the aromatic ligand coordinated to another face of the macrocycle. The general principle of macrocycle supramolecular packing suggests coordination of two ligands on both faces of the macrocycle. © 2017 American Chemical Society

Supramolecular design of the trinuclear silver(I) and copper(I) metal pyrazolates complexes with ruthenium sandwich compounds via intermolecular metal−π interactions

The interaction of copper(I) and silver(I) macrocyclic pyrazolates with aromatic ligands of ruthenium sandwiches (Cp*RuInd, CpRuInd, and Ind2Ru) in solution is shown for the first time. The similar mode of coordination of macrocycles to the C6 fragment of indenyl ligand was found both in the solution and in the solid state. Complexation of macrocycles with the nonencumbered sandwiches (CpRuInd, Ind2Ru) leads to the formation of infinite stacks via alternating molecules of macrocycles and sandwich compounds as one-dimensional coordination polymers with a regular structure. Coordination mode of the indenyl ligand is independent of the second part of the ruthenium sandwich as well as of the aromatic ligand coordinated to another face of the macrocycle. The general principle of macrocycle supramolecular packing suggests coordination of two ligands on both faces of the macrocycle. © 2017 American Chemical Society

Manganа- and rhena-copper carboranes based on the medium-size non-icosahedral 5,6-dicarba-nido-decaborane

Reaction of the deprotonated medium-size non-icosahedral carborane 5,6-nido-C2B8H12 (1) with Re(CO)5Cl affords tricarbonyl anionic complexes of Re [1,1,1-(CO)3-isonido-1,2,4-ReC2B8H10]- as PPh4- 3a and tmndH- 3b salts (tmnd — N,N,N′,N′-tetramethyl-1,8-diaminonaphtaline). Treatment of [tmndH][1,1,1-(CO)3-isonido-1,2,4-MC2B8H10]- (M = Mn 2b, Re 3b) with the equivalent amount of CuCl and PPh3 in CH2Cl2 leads to formation of two isomers of bimetallic complexes [1,3,7(6)-{Cu(PPh3)}-3,7(6)-μ-H2-1,1,1-(CO)3-isonido-1,2,4-MC2B8H8] (M = Mn 4, Re 5) with two B-H⋯Cu bonds. All newly obtained compounds were characterized by a combination of analytical and multinuclear NMR spectroscopic data and IR spectroscopy. The structures of complexes 3b and 4 were researched by X-ray diffraction studies. The nature of interaction between {Cu(PPh3)} and mangana-carborane fragments was clarified based on the computed electron density critical points (within QTAIM framework) and Density Overlap Regions Indicator (DORI) distributions. Transition state between the two diastereomers of 4 was located, the isomerization rate was found to be of order of 1 s−1. © 2020 Elsevier B.V

Coordination Chemistry of Anticrowns. Isolation of the Chloride Complex of the Four-Mercury Anticrown {[(o,o′-C6F4C6F4Hg)4]Cl}- from the Reaction of o,o′-Dilithiooctafluorobiphenyl with HgCl2 and Its Transformations to the Free Anticrown and the Complexes with o-Xylene, Acetonitrile, and Acetone

The paper reports that the interaction of o,o′-dilithiooctafluorobiphenyl with HgCl2 in ether results in the formation of the lithium chloride complex Li{[(o,o′-C6F4C6F4Hg)4]Cl} (11) of the four-mercury anticrown (o,o′-C6F4C6F4Hg)4 (12) along with the earlier isolated and characterized three-mercury anticrown (o,o′-C6F4C6F4Hg)3 (2). The complex was identified by the reaction with 12-crown-4 and determination of the structure of the [Li(12-crown-4)2]{[(o,o′-C6F4C6F4Hg)4]Cl} (13) formed. According to an X-ray analysis, the chloride anion in 13 is simultaneously coordinated with all four Hg centers of the anticrown, forming with them a pyramidal Hg4Cl fragment. The reaction of 11 (in the form of an acetonitrile solvate, 11·nMeCN) with boiling water leads to removal of LiCl from 11 and to the formation of free anticrown 12, the subsequent recrystallization of which from o-xylene affords the o-xylene complex {[(o,o′-C6F4C6F4Hg)4](o-Me2C6H4)2} (14). The obtained 14 forms in the crystal infinite chains consisting of alternating anticrown units and bridging o-xylene moieties. Another o-xylene molecule in each macrocyclic fragment of the chain plays the role of a terminal ligand. In both cases, the o-xylene ligands in 14 are bonded to only one Hg center of the corresponding mercuramacrocycle. The back-conversion of complex 14 into 12 and o-xylene proceeds in the course of its thermal decomposition under vacuum at 100-120 °C. The reaction of 12 with acetonitrile yields the nitrile complex {[(o,o′-C6F4C6F4Hg)4](MeCN)2} (15), which also forms infinite polymeric chains in the crystal. In each monomeric unit of the chain, the corresponding bridging nitrile is bonded to only one mercury atom of the anticrown moiety, whereas the other nitrile ligand is coordinated with two Hg sites. The synthesis and structure of the complex {[(o,o′-C6F4C6F4Hg)4](Me2CO)2(H2O)} (16), containing two acetone and one water ligand per molecule of 12, are also reported. Each acetone molecule in 16 interacts with only one Hg atom of 12, while the water molecule is coordinated with two mercury centers and, in addition, forms H-bonds with the oxygen atoms of the acetone species. © 2017 American Chemical Society

Isomeric commo-Ferracarboranes: meso-, dd/ll-[PPh3R][commo-Fe(2,4-closo-C2B8H10)2] and Their Bimetal Ferra–Copper Zwitterion Derivatives

The reaction of [Na][C2B8H11] with anhydrous FeCl2 in THF affords a mixture of dd/ll and meso isomers of anionic paramagnetic commo-ferracarborane [Ph3PR][commo-1,1′-Fe(closo-2,4-C2B8H10)2] (meso, R = Me: 1a; meso, Et: 1b; dd/ll, R = Me: 2a; dd/ll, R = Et: 2b) with unusual closo geometry. Both dd/ll and meso isomers were successfully isolated and their structures were determined using single-crystal X-ray diffraction studies. Their paramagnetic properties were confirmed with EPR spectra and their oxidative–reductive properties were investigated using cyclic voltammetry. It was shown that facile dd/ll → meso and meso → dd/ll transformations, leading to equilibrium in CH2Cl2 solution, occur. Quantum-chemical calculations of the isomer-to-isomer transformations were performed. Ferra–copper zwitterionic complexes [3,3′,6,7′-exo-{Ph3PCu}-3,3′,6,7′-(µ-H)4-commo-1,1′-Fe(2,4-C2B8H8)2] and [3,3′,6,6′-exo-{Ph3PCu}-3,3′,6,6′-(µ-H)4-commo-1,1′-Fe(2,4-C2B8H8)2] were synthesized and their structures were determined by single-crystal X-ray diffraction studies. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei