<?xml version="1.0" encoding="utf-8"?>
<export-example>
  <doc>
    <id>5546</id>
    <completedYear/>
    <publishedYear>2004</publishedYear>
    <thesisYearAccepted/>
    <language>eng</language>
    <pageFirst>8617</pageFirst>
    <pageLast>8625</pageLast>
    <pageNumber/>
    <edition/>
    <issue>26</issue>
    <volume>43</volume>
    <type>article</type>
    <publisherName>American Chemical Society</publisherName>
    <publisherPlace>Washington, DC</publisherPlace>
    <creatingCorporation/>
    <contributingCorporation/>
    <belongsToBibliography>1</belongsToBibliography>
    <completedDate>--</completedDate>
    <publishedDate>--</publishedDate>
    <thesisDateAccepted>--</thesisDateAccepted>
    <title language="eng">The Crucial Role of the Diphosphine Heteroatom X in the Stereochemistry and Stabilization of the Substitution-Inert [M(N)(PXP)]2+ Metal Fragments (M = Tc, Re; PXP = Diphosphine Ligand)</title>
    <abstract language="eng">The nature of the heteroatom X incorporated in the five-membered PXP-diphosphine bridging chain was found to play a primary unit role both in the overall stability and in the stereochemical arrangement of nitrido-containing [M(N)(PXP)]2+ metal fragments (M = Tc, Re). Thus, by mixing PXP ligands with labile [Re(N)Cl4]- and Tc(N)Cl2(PPh3)2 nitrido precursors in CH2Cl2/MeOH mixtures, a series of neutral M(N)Cl2(PXP) complexes (M = Tc, 1-5; M = Re, 8, 9) was collected. In the resulting distorted octahedrons, PXP adopted facial or meridional coordination, and combination with halide co-ligands produced three different stereochemical arrangements, that is, fac,cis, mer,cis, and mer,trans, depending primarily on the nature of the diphosphine heteroatom X. When X = NH, mer,cis-Tc(N)Cl2(PNP1), 1, was the only isomer formed. Alternatively, when a tertiary amine nitrogen (X = NR; R = CH3, CH2CH2OCH3) was introduced in the bridging chain, fac,cis-M(N)Cl2(PN(R)P) complexes (M = Tc, 2, 3; M = Re, 8f) were obtained. Isomerization into the mer,cis-Re(N)Cl2(PN(R)P), 8m, species was observed only in the case of rhenium when the tertiary amine group carried the less encumbering methyl substituent. fac,cis-Tc(N)Cl2(PSP), 4f, was isolated in the solid state when X = S, but a mixture of fac,cis-Tc(N)Cl2(PSP) and mer,trans-Tc(N)Cl2(PSP), 4m, isomers was found in equilibrium in the solution state. A similar equilibrium between fac,cis-M(N)Cl2(POP) (M = Tc, 5f; M = Re, 9f) and mer,trans-M(N)Cl2(POP) (M = Tc, 5m; M = Re, 9m) species was detected in POP-containing complexes. The molecular structure of all of these complexes was assessed by means of conventional physicochemical techniques including multinuclear NMR spectroscopy and X-ray diffraction analysis of representative mer,cis-Tc(N)Cl2(PN(H)P), 1, fac,cis-Tc(N)Cl2(PSP), 4f, and mer,cis-Re(N)Cl2(PN(Me)P), 8m, compounds.</abstract>
    <parentTitle language="eng">Inorganic Chemistry</parentTitle>
    <identifier type="old">5886</identifier>
    <identifier type="doi">10.1021/ic049139r</identifier>
    <identifier type="issn">0020-1669</identifier>
    <identifier type="issn">1520-510X</identifier>
    <enrichment key="bibliotheksstandort">Sonderstandort: Publica-Schrank</enrichment>
    <enrichment key="date_peer_review">06.01.2005</enrichment>
    <author>F. Tisato</author>
    <author>F. Refosco</author>
    <author>M. Porchia</author>
    <author>C. Bolzati</author>
    <author>G. Bandoli</author>
    <author>A. Dolmella</author>
    <author>A. Duatti</author>
    <author>A. Boschi</author>
    <author>C. M. Jung</author>
    <author>H.-J. Pietzsch</author>
    <author>Werner Kraus</author>
    <collection role="literaturgattung" number="">Verlagsliteratur</collection>
    <collection role="fulltextaccess" number="">Physisches Exemplar in der Bibliothek der BAM vorhanden ("Hardcopy Access")</collection>
  </doc>
</export-example>
