Das vollständige Manuskript dieser Zuschrift erscheint in: Angew. Chem. Suppl. 1982, 411. DOI: 10.1002/ange.198204110

Treatment of the solvento species [Rh(C8H12) (solvent)2][SbF6] (solvent = methanol, ethanol, or tetrahydrofuran) with a twice-molar amount of the diphosphazane ligands (RO)2PN(R')P(OR)2 (R' = Me or Et; R = Me, Et, or Pr(i)) in the appropriate solvent leads to the ready formation of monocationic [Rh{(RO)2PN(R')P(OR)2}2]+ and/or dicationic [Rh2{mu -(RO)2PN(R')P(OR)2} 2{(RO)2PN(R')P(OR)2} 2]2+ hexafluoroantimonate salts, with the tendency to afford dinuclear derivatives decreasing along the series Me > Et > Pr(i). Carbon monoxide readily forms addition products with these ionic species, giving rise to five-coordinate derivatives of the type [Rh(CO) { (RO)2PN(R')P(OR)2}2][SbF6] in the case of the mononuclear derivatives, and inserting across the two rhodium atoms to afford [Rh2(mu-CO) {mu-(MeO)2PN(Et)P(OMe)2}2{(MeO)2PN(Et)P(OMe)2}2][SbF6]2 in the case of [Rh2{mu-(MeO)2PN(Et)P(OMe)2}2{(MeO)2PN(Et)P(OMe)2}2] [SbF6]2. These mono- and dicationic derivatives also react readily with iodine affording [RhI2{(RO)2PN(R')P(OR)2}2][SbF6] and [Rh2(mu-I){mu-(MeO)2PN(Et)P(OMe)2}2{(MeO)2PN(Et)P(OMe)2}2] [SbF6]n (n = 2 or 3) respectively. The coordination behaviour of the diphosphorus ligands (MeO)2PCH2P(OMe)2 and Me2PCH2PMe2 towards [Rh(C-8H12) (solvent)2] [SbF6] has also been investigated.

Compounds RXHal2 (X = P, As, Sb) react with Na2[M2(CO)10] (M = Cr, Mo, W) to yield three types of products: A, [(CO)5M]2X-R containing trigonally planar coordinated X; C, [(CO)5M]3X-R containing coordinated metallacyclic ligands; B, [xxx] D, [(CO)5M]n (R)X = X (R) (n = 0, 1, 2, 3). The relation between these species, especially the one based on the valence tautomerism between A und B, is experimentally verified. Preparative, spectroscopic and X-Ray-structural results reveal a consistent picture of the relevant chemistry.

Preparation des complexes [(CO) 5 M] 2 X-R, [(CO) 5 M] 3 X-R, L n M-L n M-X(R) et [(CO) 5 M] n (R)X=X(R). Structures moleculaires (X=P, As, Sb)

The trihalophosphane complexes LnMPHal3 (LnM = Cp(CO)2Mn, (CO)5Cr, (CO)5W; Hal = Cl, Br), upon treatment with Co2(CO)8, mainly yield clusters of the type Co3(CO)9(μ4-P)MLn with the (μ3-P)Co3(CO)9) unit acting as ligand. The analogous arsenic compound Co3(CO)9(μ4-As)Cr(CO)5 is obtained from the arsinidine complex [(CO)5Cr]2AsCl with NaCo(CO)4. In addition to the syntheses and reactios of these clusters several reactions leading to clusters with μ4-P-, μ4-As-, μ4-PR- and μ2-PR2 groups by reductive dehalogenation of coordinated halophosphanes are reported. The different types of compounds are documented by six X-ray-structure analyses.

Arsinidenkomplexe (III) entstehen besonders einfach durch Reaktion von (I) mit den Arsinen (II).

Reactions of Fe2(CO)9 with LnMPHal3 (LnM = 16-electron fragment: Cp(CO)2Mn, (CO)5Cr, (CO)5Mo, (CO)5W) yield clusters of the type F3(CO)9(μ4-P)2(MLn)2 (II). Compounds II contain the trigonal bipyramidal cluster framework Fe3(CO)9(μ3-P)2, the basis of which is a closed triangle formed by three Fe(CO)3 units; the apical positions of the trigonal bipyramid are occupied by phosphorus atoms. Each of the capping phosphorus atoms binds an additional MLn fragment. Compounds of type II are also obtained from Fe2(CO)6(μ3-P)2(MLn)2 (I) by formal addition of an Fe(CO)3 group. A further general synthetic approach to clusters Fe3(CO)9(μ4-X)2 (MLn)2 (X = P, As, Sb) is the reaction of halo-phosphinidene, arsinidene or stibinidene complexes, (LnM)2XHal (X = P, As, Sb) with Na2Fe(CO)4.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDiarsenic, As2, as a 4-, 6-, or 8-electron donor ligandGottfried Huttner, Beate Sigwarth, Olaf Scheidsteger, Laszlo Zsolnai, and Olli OramaCite this: Organometallics 1985, 4, 2, 326–332Publication Date (Print):February 1, 1985Publication History Published online1 May 2002Published inissue 1 February 1985https://pubs.acs.org/doi/10.1021/om00121a023https://doi.org/10.1021/om00121a023research-articleACS PublicationsRequest reuse permissionsArticle Views158Altmetric-Citations67LEARN 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

AbstractDie Titel‐Arsiniden‐ bzw. ‐Stibiniden‐Komplexe [(CO)5M]2XR, in denen die Ligandgruppierung RX durch π‐Wechselwirkung mit den 16‐Elektronenfragmenten M(CO)5 stabilisiert sind, bilden mit Lewisbasen L stabile Addukte.

In (LnM)2X-Hal compounds which contain a trigonally planar coordinated bridging element (X = P, As, Sb) stabilized by two 16-electron LnM fragments the halogen may be substituted by monovalent organometallic groups. In the resulting molecules the bridging X atoms are coordinated to three metal atoms in a trigonal planar fashion. The syntheses and properties of 12 species of this type (I–IX) are described.

Treatment of [Rh2Cl2(CO)2 {μ-(PhO)2PN(Et)P(OPh)2}2] with various reducing agents gives a number of products, the type depending on the conditions employed. The products isolated include [Rh2(CO)2{μ-(PhO)2PN(Et)P(OPh)2}2], [Rh2(CO)3{μ-(PhO)2PN(Et)P(OPh)2}2],and [Rh2HgCl(μ-H)(CO)2{μ-(PhO)2PN(Et)P(OPh)2}2]; the structure of the last complex was determined by X-ray diffraction.

Reaction of [Fe2(CO)9] with a half molar amount of R2PYPR2 (Y = CH2, R = Ph, Me, OMe or OPri; Y = N(Et), R = OPh, OMe or OCH2; Y = N(Me), R = OPri or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe2(μ-CO)(CO)6{μ-R2PYPR2}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe2(μ-CO)(C))4{μ-R2PYPR2}2] but under thermal conditions in the formation of the mononuclear species [Fe(CO)3{R2PYPR2}]. Reaction of [Ru3(CO)12] with an equimolar amount of (RO)2PN(R′)P(OR)2 (R′ = Me, R = Pri or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru3(CO)10{μ-(RO)2PN(OR)2}] which reacts further with excess (RO)2PN(R′)P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound [Ru2(μ-CO)(CO4{μ-(RO)2PN(R′)P(OR)2}2]. The molecular structure of [Ru2(μ-CO)(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2], which has been determined by X-ray crystallography, is described.

Treatment of [Rh2Cl2(CO)2 {μ-(PhO)2PN(Et)P(OPh)2}2] with various reducing agents gives a number of products, the type depending on the conditions employed. The products isolated include [Rh2(CO)2{μ-(PhO)2PN(Et)P(OPh)2}2], [Rh2(CO)3{μ-(PhO)2PN(Et)P(OPh)2}2],and [Rh2HgCl(μ-H)(CO)2{μ-(PhO)2PN(Et)P(OPh)2}2]; the structure of the last complex was determined by X-ray diffraction.

AbstractDurch Reaktion von Arsiniden‐ Komplexen (I) mit metallorganischen Nucleophilen (II) erfolgt erstmals die Synthese von Verbindungen (III), in denen alle fünf Valenzelektronen eines uyverbrückenden As‐Atoms in die Bindung zu drei Metall‐Ligand‐Fragmenten einbezogen sind.

AbstractDas Distickstoffhomologe Sb, existiert nur bei hohen Ternp.

AbstractDer Wolframdiarsen‐carbonyl‐Komplex (III) entsteht bei der Umsetzung von Arsentrichlorid (II) mit den Wolfram‐carbonyl‐Verbindungen (I) oder (IV).