Structural studies of coordination compounds. A joint NQR and x-ray investigation of trialkylphosphine-gallium trichloride adducts

Carter, John C.; Jugie, Gérard; Enjalbert, R.; Galy, J.

doi:10.1021/ic50183a030

Cited by 56 publications

(27 citation statements)

References 36 publications

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“…The complex shows Q symmetry with the center of inversion located in the middle of the C=C double bond. The Ga-P distance [2.4008(2) Ä] is almost identical with literature values for R 3P-G aX3 com pounds [8,10], The GaBr3 unit is tilted towards the C=C double bond as shown by the smaller angle C l-P-G a [102.8(5)°] as compared with C211-P-Ga The crystals of compound 2 are monoclinic, space group P2i/c with Z = 4 molecules in the unit cell. Only one phosphorus atom (P 1) is coordinated to the metal atom.…”

Section: Structural Investigationssupporting

confidence: 84%

Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene

Sigl

Schier

Schmidbaur

1998

Zeitschrift Für Naturforschung B

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Z-l,2-Bis(diphenylphosphino)ethene, cis-Ph2PCH=CHPPh2, forms 1:2 adducts with GaBn and GaL, the former of which has been identified in an X-ray diffraction study as the complex of the isomerized ligand, E-Ph2PCH=CHPPh2. The GaL complex is believed to be analogous on the basis of analytical and spectroscopic data. InBr3 affords a 1 :1 complex with an ionic structure [(Ph2PCH=CHPPh2)2lnBr2]+ [InBr4]_ in which the cation contains the original cisligand. With Inl^ also a 1:1 adduct is obtained, where the metal triiodide unit is attached to only one phosphorus atom of the non-isomerized (cis) ligand in the solid state. There is rapid site exchange of the Inl3 unit in chloroform solution as followed by NMR spectroscopy. -The metal halide induced Z/E isomerization of Ph2PCH=CHPPh2 has been studied in various solvents and at variable temperature with stoichiometric and catalytic amounts of AIX3 and GaX3 Lewis-acids. InX3 compounds proved ineffective (X = Cl, Br, I). Anhydrous AlBr3 was found to be most efficient, giving a 90% Z/E conversion in 10 min at 100°C in toluene. A mechanism is proposed which is compatible with the experimental data.

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Section: Structural Investigationssupporting

confidence: 84%

Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene

Sigl

Schier

Schmidbaur

1998

Zeitschrift Für Naturforschung B

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“…However, there seem to be only small effects on the Ga-E bond lengths from changing the R group, although in analogous complexes with R = aryl the Ga-E seem to be marginally longer than R = alkyl [170][171][172][173][174][175][176][177], which is in keeping both with the Ga-X bonds being dominant compared to Ga-E, and also with the absence of significant steric effects in these complexes. There appear to be no established examples of gallium(III) halide complexes of stibines; early studies suggested fragmentation of the stibine or X/R exchange [7].…”

Section: Galliummentioning

confidence: 77%

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

Burt

Levason

Reid

2014

Coordination Chemistry Reviews

104

137

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“…Die beobachtete Fünffach-Koordination des Al-und In-Komplexes gegenüber der Vierfach-K oordination beim ansonsten gleichen Ga-Komplex hat erstaunliche Parallelen bei den Phosphanaddukten der Trichloride M Cl3(PMe3)2 (M = A1, In) und G aC l3(PM e3) [3,9], wobei die Ursachen ähnlich sein dürften. Auch bei Phosphinomethanid-Komplexen des zweiwertigen Si, Ge und Sn wurden im übrigen ähnlich augenfällige U nter schiede in den Koordinationszahlen beobachtet [37].…”

Section: Abb 4 Molekülstruktur Vonunclassified

“…Bei Ph2PC H 2PPh2(M R 3) (M = Al, R = Me; M = Ga, R = Me, Et) und bei Ph2PC H 2PPh2(G aM e2Cl) konnten allerdings auch bei tiefen Tem peraturen lediglich rasch fluktuierende unsymmetrische Addukte beobachtet werden [6]. Auch vom Indium [7] sind mit O rganophosphanen 1:2 Komplexe des Typs InX 3(PR 3)2 (X = Halogenid, R = Alkyl, Aryl) [3,8] bekannt, beim Gallium wurde G aC l3(PM e3) [3,9] beschrieben. Die Komplexchemie von Organothallium-Verbindungen ist weniger gut ausge baut [1].…”

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Vier- und fünffach koordinierte Organometall-Phosphankomplexe von Aluminium, Gallium, Indium und Thallium / Four- and Five-Coordinate Organometal Phosphine Complexes of Aluminum, Gallium, Indium, and Thallium

Müller¹,

Lachmann²

1993

Zeitschrift Für Naturforschung B

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A nionic Benzylphosphines, Main Group Metals, Phosphine Complexes, Crystal Structure The organom etal phosphine complexes M L3 (L = [o-(Ph2PCH2)C6H4]"; M = A l3+, G a3+, In3+) are obtained from MC13 and the lithiated ligand in diethyl ether. Tl[o-(Ph2PC H 2)C6H 4]3 is prepared from T1C1 by a disproportionation reaction. M 1 species could not be detected with L as ligand. Al[o-(Ph2PCH 2)C6H4]3 is the first triorganoaluminum bis(phosphine) adduct where C3P2 pentacoordination at aluminum has been definitely proven for both the solution (<5(27A1) = 131 ppm, w 1/2 = 12 kHz) and the solid state (d (A l-P ) = 2.676(3)/2.782(2) Ä). The trigonal-bipyramidal coordination geometry (C3P2) at Al is achieved by two o f the anionic phosphines acting as chelating ligands, spanning equatorial (C atoms) and axial sites (P atom s), while the third phosphine is only carbon-bonded. Like A1L3, the heavier congeners M L3 (M = G a, In, Tl) are stereochemically nonrigid molecules in solution. Surprisingly, in the solid state only InL3 resembles the aluminum complex (C3P2 penta-coordination) while G aL 3 and T1L3 contain four-coordinate metal centers (C3P). This may be rationalized by the notice ably less polar G a -P bonds as compared to A l-P and I n -P bonds, while in T1L3 the span o f the ligand is not sufficient to allow for chelating coordination at a five-(or six-)coordinate Tl center. Koordinationszahlen größer als vier werden bei Komplexen des dreiwertigen Aluminiums, Galli ums, Indium s und Thalliums vor allem mit kleinen "harten" D onorzentren, wie Stickstoff, Sauerstoff und einigen Halogeniden beobachtet [1]. So lassen sich neutrale fünffach-koordinierte Alum inium komplexe A1X3L2 (L = Lewis-Base; X = Haloge nid, Alkyl, Hydrid) vor allem mit D onoren L mit einem Stickstoff-Donorzentrum isolieren [2], Mit den weniger nukleophilen Organophosphanen als D onor scheinen stabile Vertreter au f AlCl3(PM e3)2 [3] und ein kürzlich beschriebenes 1:2 A lH 3-Phosphan-A ddukt [4] beschränkt zu sein. Fünffach-K oordination des Aluminiums in Triorganoalum inium -Phosphanaddukten wurde für 1:1 Addukte mit D iphosphanen postuliert [5]. Bei Ph2PC H 2PPh2(M R 3) (M = Al, R = Me; M = Ga, R = Me, Et) und bei Ph2PC H 2PPh2(G aM e2Cl) konnten allerdings auch bei tiefen Tem peraturen lediglich rasch fluktuierende unsymmetrische Ad-* Sonderdruckanforderungen an Prof. Dr. G. Müller. Verlag der Zeitschrift für Naturforschung, D-72072 Tübingen 0 9 3 2 -0 7 7 6 /9 3 /1 1 0 0 -1 5 4 4 /$ 01.00/0 dukte beobachtet werden [6]. Auch vom Indium [7] sind mit O rganophosphanen 1:2 Komplexe des Typs InX 3(PR 3)2 (X = Halogenid, R = Alkyl, Aryl) [3, 8] bekannt, beim Gallium wurde G aC l3(PM e3) [3, 9] beschrieben. Die Komplexchemie von Organothallium-Verbindungen ist weniger gut ausge baut [1].Im Gegensatz zu neutralen Phosphanen sind an ionische Phosphane als gute Kom plexbildner auch gegenüber p-Block-Elementen bekannt. Dies konnte vor allem anhand von Phosphinom ethaniden gezeigt werden, bei denen die carbanionoide Funktion direkt mit dem Phosphinorest verknüpft...

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Structural studies of coordination compounds. A joint NQR and x-ray investigation of trialkylphosphine-gallium trichloride adducts

Cited by 56 publications

References 36 publications

Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene

Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

Vier- und fünffach koordinierte Organometall-Phosphankomplexe von Aluminium, Gallium, Indium und Thallium / Four- and Five-Coordinate Organometal Phosphine Complexes of Aluminum, Gallium, Indium, and Thallium

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