F. M. Dolgushin

Chemistry of vinylidene complexes. XIII. The reaction between Cp(CO)2MnPt(μ-CCHPh)(η2-dppm) and Fe2(CO)9: simultaneous formation of the μ3-vinylidene MnFePt and μ4-vinylidene PtFe3 clusters. Crystal structure of (η5-C5H5)MnFePt(μ3-CCHPh)(CO)6[η1-Ph2PCH2P(O)Ph2] ☆ ☆☆

Abstract The reaction between [Cp(CO)2MnPt(μ-CCHPh)(η2-dppm)] 2 (1) and [Fe2(CO)9] gives heterometallic MnFePt and PtFe3 vinylidene clusters 2–4, in which diphosphine ligands are coordinated to metal cores in three different modes. In [(η2-dppm)PtFe3(μ4-CCHPh)(CO)9] (2) the Pt atom is chelated by dppm while in [CpMnFePt(μ3-CCHPh)(μ-dppm)(CO)5] (3) dppm bridges the Pt–Fe bond. Complex 3 was shown to exist in two isomeric forms. The novel complex {CpMnFePt(μ3-CCHPh)(CO)6[η1-Ph2PCH2P(O)Ph2]} (4), characterized by X-ray diffraction study, possesses a trimetallic chain core. The diphosphine ligand in 4 links to platinum by only one of phosphorus atoms whereas the second P atom is uncoordinated and oxidized to the phosphineoxide group.

Interaction of carbon dioxide with the bis(trimethylsilyl)acetylene complex of permethyltitanocene: synthesis and structure of the binuclear carbonate complex of permethyltitanocene (Cp2∗Ti)2CO3

Abstract It has been shown that in the interaction of carbon dioxide with the bis(trimethylsilyl)acetylene complex of permethyltitanocene Cp 2 ∗ Ti(Me 3 SiC 2 SiMe 3 ), full displacement of bis(trimethylsilyl)acetylene from the titanium coordination sphere takes place and carbon dioxide undergoes disproportionation to form Cp 2 ∗ Ti(CO) 2 and the binuclear carbonate complex of permethyltitanocene (Cp 2 ∗ Ti) 2 CO 3 . The structure of (Cp 2 ∗ Ti) 2 CO 3 has been established by X-ray diffraction study. Structural data on the related chlorine-containing carbonate complex Cp 2 ∗ Ti(Cl)CO 3 TiCp 2 ∗ are also reported.

Complexation of trimeric copper(i) and silver(i) 3,5-bis(trifluoromethyl)pyrazolates with amine-borane

A complexation of trimeric copper(i) and silver(i) 3,5-bis(trifluoromethyl)pyrazolates ((ML)3) with BH3NEt3 was studied by IR spectroscopy in hexane and dichloromethane solutions. In hexane, two complexes [(ML)3][BH3NEt3]2 (1) and [(ML)3][BH3NEt3] (2) were formed depending on the ratio of reagents. In dichloromethane, only one complex [(ML)3][BH3NEt3] (2) was found. The thermodynamic parameters (ΔH○, ΔS○) of complex 1 in hexane and complex 2 in dichloromethane were obtained. The complex [(AgL)3][BH3NEt3] was isolated in the solid state, its structure was established by X-ray diffraction. The complex is formed due to two bridges B-H-Ag, one BH group is not involved in the complexation. In crystal, molecules 2 form supramolecular dimers due to the intermolecular interactions between metals of two macrocycles.

Formation of “three-bridge” cobalt-copper commo-cluster with the (B-H)3...Cu bond in the reaction of [Cs][commo-3,3′-Co(1,2-C2B9H11)2] with copper(i) and copper(ii) compounds

Zwitterionic 4,8,8′-exo-{Ph3PCu}-4,8,8′-(μ-H)3-commo-3,3′-Co(1,2-C2B9H9)-(1′,2′-C2B9H10) and ionic [(PPh3)3Cu][commo-3,3′-Co(1,2-C2B9H11)2 complexes were synthesized in moderate yields by the reaction of anionic commo-complex [Cs][commo-3,3′-Co-(1,2-C2B9H11)2]) in a CH2Cl2 solution with anhydrous CuCl2 or CuCl in the presence of PPh3. The complexes were also synthesized by alternative methods and characterized by NMR and X-ray diffraction methods.

First cupracarborane commo-clusters based on the medium-cage nido-5,6-C2B8H12-carborane and molecular structure of [Ph3PEt][commo-9,9′-Cu(nido-7,8-C2B8H11)2]

A reaction of anhydrous CuCl2 with Na salts of the medium-cage carborane [7-X-nido-5,6-C2B8H10]−(X = H or I) derivatives in THF leads to new cupracarborane commo-clusters, [commo-9,9′-Cu(nido-7,8-C2B8H11)2]− and [commo-9,9′-Cu(11-I-nido-7,8-C2B8H10)2]−, in moderate yields. The clusters were isolated as stable [Ph3PEt]+ salts and characterized by 1H, 31P{1H}, and 11B/11B{1H} NMR spectroscopy and X-ray crystallography (for the unsubstituted derivative). The use in this reaction of the reducing agent Na2SO3 considerably increases the yields of both complexes from 25 and 18% to 74 and 68%, respectively.

Metallacarborane clusters based on the middle-cage carborane [5,6-nido-C2B8H12]. Synthesis and the thermal isonido-to-closo rearrangement of the anionic complex [PPN][commo-1,1′-Rh(7-MeO-isonido-2,4-C2B8H9)-(isonido-2,4-C2B8H10)]

The reaction of the middle-cage carborane 5,6-nido-C2B8H12 with the dimeric rhodium complexes [(η2-C8H14)2RhCl]2 or [(η4-C8H12)RhCl]2 in a MeOH/C6H6 mixture gave the anionic commo-rhodacarborane [PPN][commo-1,1′-Rh(isonido-2,4-C2B8H10)2] (as a mixture of meso and dd/ll isomers) and its 7-B-methoxylated derivative [PPN][commo-1,1′-Rh(7-MeO-isonido-2,4-C2B8H9)(isonido-2,4-C2B8H10)] in moderate yields. The latter was subjected to the thermal isonido-to-closo rearrangement to form the new commo-cluster [PPN][commo-1,1′-Rh(closo-2,3-C2B8H9OMe)(closo-2,3-C2B8H10)]. The newly synthesized compounds were characterized by NMR spectroscopy and X-ray diffraction.

Coordination chemistry of anticrowns. Complexation of cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)3 with compounds containing an active methylene group

The reactions of three-mercury anticrown (o-C6F4Hg)3 (1) with acetoacetic ester (AE), malonic ester (ME), and malonodinitrile (MN) afford 1: 1 complexes {[(o-C6F4Hg)3](AE)} (3), {[(o-C6F4Hg)3](ME)} (4), and {[(o-C6F4Hg)3](MN)} (5). The structures of complexes 3–5 were determined by X-ray diffraction analysis. Complex 3 has a discrete structure in the solid state, whereas complexes 4 and 5 form in the crystal extended stacks representing polydecker sandwiches with alternating molecules of 1 and ME or MN. According to the X-ray diffraction and IR spectral data, the molecule of AE in complex 3 is in the keto form.

Reactions of dodecacarbonyltriruthenium with unsaturated α,β-diketones

Reactions of Ru 3 (CO) 12 with endiones trans -ArCOCH=CHCOAr, Ar = Ph, p -MeC 6 H 4 were studied. Three isomeric complexes were isolated from reactions with each of the ligands. All isomers involve one and the same central bicylic fragment, as well as two peripheral oxaruthenacycles, concatenated with the central fragment via spiro metal atoms. The isomers differ from each other by the orientation of the peripheral metallacycles relative to the central bicyclic moiety. The structures of the two complexes have been established by means of single crystal X-ray diffraction studies.

Cyclopentadienyl derivatives of octahedral carbonylcarbide hexaruthenium clusters: synthesis, NMR, IR and X-ray characterization

Abstract The reaction of hexanuclear carbonylcarbide cluster Ru6C(CO)17 (1) with pentamethylcyclopentadiene by reflux in heptane leads to a new chelate cluster Ru6C(μ-η1-η5-CH2C5Me4)(CO)14 (2). The compound 2 contains a CH2 group α-bonded to one of the Ru atoms in the Ru6 cluster and a C5Me4-ligand η5-coordinated by the adjacent Ru atom of the Ru6 cluster. Reflux of 1 in hexane with two molecular equivalents of nickelocene, Ni(C5H5)2  NiCp2, used as a source of cyclopentadiene yields the Ru6C(CO)12Cp2 (3) cluster. The compounds 2 and 3 have been characterized by NMR and IR spectroscopy and their crystal structures determined by X-ray diffraction studies.

Orientation in the metalation of amide, carbamate, ureido, and allylic derivatives of cymantrene

The orientation in the metalation of monosubstituted carbamate-, amide-, ureido-, and allyl-containing derivatives of cymantrene was determined for the first time. The data obtained open up a synthetic route to polyfunctional 1,2- and 1,3-disubstituted cymantrenes. They can serve as the starting materials for the preparation of chelate complexes of (dicarbonyl)-(cyclopentadienyl)manganese, which hold promise as novel organometallic photochromes. A method for the synthesis of earlier unknown chiral derivatives of cymantrene with a quaternary carbon atom in position 1 of the side chain was proposed.