The reactions of tetetrahedral mixed-metal cluster [NEt4][RuCo3(CO)12] 1 with [NO][BF4] afforded the nitrosyl-substituted cluster [RuCo3(Co)11(NO)] 3 in high yield. The latter reacts with excess alkynes RC2R' to give [RuCo3(Co)9(NO)(mu-4-eta-2-RC=CR')](R = R' = Ph 4a; R = Ph, R' = H 4b; R = R' = H 4c) via specific insertion in a Co-Co bond, together with a small amount of the corresponding trinuclear cluster [RuCo2(CO)9(mu-3-eta-2-RC=CR')] (R = R' = Ph 5a; R = Ph, R' = H 5b; R = R' = H 5c). All the complexes have been characterised by IR, UV/VIS, H-1 and Co-59 NMR spectroscopy. The crystal structures of 3 and 4b have been determined by X-ray diffraction methods. Complex 3 exhibits a RuCo3 tetrahedron and the linear nitrosyl ligand is axially bonded to one of the Co atoms of the Co3 base. The structure of 4b consists of a RuCo3 butterfly in which the ruthenium atom occupies a hinge position, the alkyne ligand having been incorporated into the cluster core to generate a closo-RuCo3C2 octahedral framework.

The mixed-metal cluster compounds [MPt3(μ-CO)3(PPh3)5]X (M  Cu, X  BF4; M  Ag, X  NO3; M  Au, X  PF6) have been synthesized in high yields from [Pt(PPh3)2(C2H4)] and group 11 reagents. The copper-platinum cluster [CuPt3(μ-CO)3(PPh3)5]BF4 has been characterized by X-ray diffraction. It adopts a distorted tetrahedral geometry with the Cu(PPh3) group capping the Pt3 face, one Pt atom of which is bonded to two PPh3 ligands.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSyntheses and dynamic stereochemistry of hydrido-carbonyl heterobinuclear metal-metal bonded complexes. Crystal structures of MoPt(H)(.eta.-C5H5)(CO)3(PPh3)2 (Mo-Pt) and MnPt(.mu.-H)(.mu.-CO)(CO)4(PEt3)2 (Mn-Pt)Odile Bars, Pierre Braunstein, Gregory L. Geoffroy, and Bernard MetzCite this: Organometallics 1986, 5, 10, 2021–2030Publication Date (Print):October 1, 1986Publication History Published online1 May 2002Published inissue 1 October 1986https://pubs.acs.org/doi/10.1021/om00141a015https://doi.org/10.1021/om00141a015research-articleACS PublicationsRequest reuse permissionsArticle Views104Altmetric-Citations26LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

AbstractThe trans‐ or cis‐compound (I) or (III) reacts with PMe2Ph to give the complex (II) or (IV) (no yield given), which exist in a single isomeric form in the solid state.

Hexafluorobut-2-yne (hfb) reacted with [M(dmba – H)2](dmba =NN-dimethylbenzylamine, M = Ni or Pd) to give [([graphic omitted]Me2)}] compounds in which one acetylene was formally inserted into one of the M–C bonds, the second metallocycle being unmodified. A cis geometry has been tentatively assigned to the compound where M = Ni, whereas a trans configuration is found for M = Pd. This latter complex isomerizes slowly in solution to give the cis isomeric form which has been studied by single-crystal X-ray diffraction measurements; the complex crystallizes in the monoclinic space group P21/n with a= 11.705(2), b= 11.146(2), c= 16.317(5)Å, β= 93.16(2)°, and Z= 4. The two nitrogen atoms are indeed mutually cis to each other, the Pd–N distances being rather long [2.231 (3) and 2.223 (3)Å]; the phenyl ring which is a part of the seven-membered palladated ring is now perpendicular to the co-ordination plane of the Pd atom. Reaction of lithiated NN-dimethylnaphthylamine (dmna) or NN-dimethylaminotoluene (dmat) with [PdCl2(SEt2)2] gave the bicyclic compounds [Pd(dmna – H)2] and [Pd(dmat – H)2], the latter in very low yield however. The former compound gave metallic Pd and an organic product by reaction with hfb. Asymmetric bicyclic compounds have been synthesized by reaction of lithiated dmna, dmat, or dmba with the chlorine-bridged dimers [{Pd(dmba – H)Cl}2] or [{Pd(8Me-quin – H)Cl}2](8Me-quin = 8-methylquinoline). Reaction between hfb and the bicyclic compound [Pd(dmba – H)(dmna – H)] afforded a compound in which again only one acetylene has reacted with the Pd–C bond of the palladated dmba moiety; the two Pd–C bonds are trans to each other and it also isomerizes into the corresponding cis species in solution. [Pd(dmba – H)(8Me-quin – H] with hfb gave a product in which the acetylene reacted with both Pd–C bonds affording a bicyclic compound with two seven-membered rings attached to the same palladium. This product exists as a mixture of cis and trans isomers but only the cis species has been isolated in a pure crystalline form. Its stereochemistry has been confirmed by an X-ray diffraction study; the complex crystallizes in the monoclinic space group P21/n with a= 13.948(8), b= 12.338(7), c= 16.868(6)Å, β= 107.89(4)°, and Z= 4. The seven-membered ring containing the dmba ligand resembles that described above whereas the new ring containing 8Me-quin – H is mainly described by two planes whose dihedral angle is 112.3°. [Pd(dmba – H)(8Me-quin – H)] also reacts under smooth conditions with MeO2CCCCO2Me to give a mixture of products from which one compound has been isolated in a pure form : it has fixed one acetylene per palladium atom and we suggest on the basis of n.m.r. data that it has reacted with the C–Pd bond of the palladated 8Me-quin moiety.

Hexafluorobut-2-yne (hfb) reacted with [M(dmba – H)2](dmba =NN-dimethylbenzylamine, M = Ni or Pd) to give [([graphic omitted]Me2)}] compounds in which one acetylene was formally inserted into one of the M–C bonds, the second metallocycle being unmodified. A cis geometry has been tentatively assigned to the compound where M = Ni, whereas a trans configuration is found for M = Pd. This latter complex isomerizes slowly in solution to give the cis isomeric form which has been studied by single-crystal X-ray diffraction measurements; the complex crystallizes in the monoclinic space group P21/n with a= 11.705(2), b= 11.146(2), c= 16.317(5)A, β= 93.16(2)°, and Z= 4. The two nitrogen atoms are indeed mutually cis to each other, the Pd–N distances being rather long [2.231 (3) and 2.223 (3)A]; the phenyl ring which is a part of the seven-membered palladated ring is now perpendicular to the co-ordination plane of the Pd atom. Reaction of lithiated NN-dimethylnaphthylamine (dmna) or NN-dimethylaminotoluene (dmat) with [PdCl2(SEt2)2] gave the bicyclic compounds [Pd(dmna – H)2] and [Pd(dmat – H)2], the latter in very low yield however. The former compound gave metallic Pd and an organic product by reaction with hfb. Asymmetric bicyclic compounds have been synthesized by reaction of lithiated dmna, dmat, or dmba with the chlorine-bridged dimers [{Pd(dmba – H)Cl}2] or [{Pd(8Me-quin – H)Cl}2](8Me-quin = 8-methylquinoline). Reaction between hfb and the bicyclic compound [Pd(dmba – H)(dmna – H)] afforded a compound in which again only one acetylene has reacted with the Pd–C bond of the palladated dmba moiety; the two Pd–C bonds are trans to each other and it also isomerizes into the corresponding cis species in solution. [Pd(dmba – H)(8Me-quin – H] with hfb gave a product in which the acetylene reacted with both Pd–C bonds affording a bicyclic compound with two seven-membered rings attached to the same palladium. This product exists as a mixture of cis and trans isomers but only the cis species has been isolated in a pure crystalline form. Its stereochemistry has been confirmed by an X-ray diffraction study; the complex crystallizes in the monoclinic space group P21/n with a= 13.948(8), b= 12.338(7), c= 16.868(6)A, β= 107.89(4)°, and Z= 4. The seven-membered ring containing the dmba ligand resembles that described above whereas the new ring containing 8Me-quin – H is mainly described by two planes whose dihedral angle is 112.3°. [Pd(dmba – H)(8Me-quin – H)] also reacts under smooth conditions with MeO2CCCCO2Me to give a mixture of products from which one compound has been isolated in a pure form : it has fixed one acetylene per palladium atom and we suggest on the basis of n.m.r. data that it has reacted with the C–Pd bond of the palladated 8Me-quin moiety.

The tetrahedral cluster NEt4[RuCo3(CO)12] was prepared in 90% yield, and on treatment with excess PhCCPh gave the “butterfly” cluster NEt4[RuCo3(μ-CO)2(CO)8(μ4-η2-PhCCPh)]. Reaction of the latter with HCl gave the neutral trimetallic cluster RuCo2(CO)9(μ3-η2-PhCCPh). Both products were characterized by single-crystal X-ray diffraction studies.

The borocarbide La5B2C6 was prepared by melting lanthanum, boron and carbon in a high frequency furnace on a water-cooled copper hearth. The crystal structure of the compound was determined by single-crystal X-ray analysis. The lattice parameters of the tetragonal cell (space group, P4 (C14, no. 75); Z = 4) are as follows: a = 8.585(3) Å and c = 12.313(2) Å. Intensity measurements were obtained using a four-circle diffractometer. The structure was solved by the Patterson method and was refined by full matrix least-squares calculations to R = 0.079 for 1305 unique structure factors. La5B2C6 is isostructural with Ce5B2C6 and undergoes a superconducting transition at 6.9 K.

AbstractDie Reaktion von lithiiertem N,N‐Dimethylnaphthylamin oder N,N‐Dimethylaminotoluol 150 mit Dichloro‐bis‐[ethylmercapto]‐palladium liefert die metallierten Produkte (II) oder (III), die Darstellung von (I) ist bekannt.

AbstractBei der Reaktion des trans‐Platinkomplexes (I) mit dem Carbonylmolybdat (II) wird der Titelkomplex (III) isoliert, der IR‐ und 1H‐ sowie 3′ P‐ NMR‐spektroskopisch charakterisiert wird.

AbstractDie neue Titelverbindung wird durch Zusammenschmelzen von Ce, Bund Cunter Ar in einem Hochfrequenzofen dargestellt.

The new compound Ce5B2C6 was prepared by melting cerium, boron and carbon in a high frequency furnace on a water-cooled copper hearth; the inert atmosphere was purified argon. The lattice parameters of the tetragonal cell were found to be a = 8.418(3) Å and c = 12.077(4) Å. The structure was determined from single-crystal counter data by Patterson and Fourier methods and refined to R = 0.052 for 640 unique structure factors. The space group is P4 (C41), Z = 4. It represents a new structural type which can be derived from the CaC2- and Sc15C19-type structures by filling the (distorted) octahedral voids alternately with carbon atoms and carbon pairs. Boron atoms are needed to stabilize the structure.

Reaction of cis-PtCl2(PPh2Cl)2 with NaMn(CO)5 in tetrahydrofuran yields new tri- and tetrametallic platinum-manganese complexes. The substitution of the PtCl and PCl bonds is accompanied by a redox reaction, a labilization of the PtP bonds as exemplified by the isolation of complexes in which such bonds have been broken or created, and the rupture of one MnCO bond.

In the framework of a systematic study of the hydrates MM'O4. nH20 (M: an element possessing an octahedral environment of O atoms, M': an element possessing a tetrahedral environment) a classification has developed which not only allows the various compounds to be placed in their structural groups, but also allows the prediction of the possible theoretical structural types. The study of the possible combinations of octahedra and tetrahedra for the monohydrates MM'O4.H20 has allowed eight different structural classes to be foreseen.