Preparation and structural studies of diphenylthiophosphinito rhodium(III) complexes. X-ray structure analysis of [{(C5Me5)Rh}2(μ-Cl)2(μ-Ph 2PS)][BPh4]

  1. Pinillos, M.T. 1
  2. Jarauta, M.P. 1
  3. Carmona, D. 1
  4. Oro, L.A. 1
  5. Apreda, M.C. 2
  6. Foces-Foaces, C. 2
  7. Cano, F.H. 2
  1. 1 Instituto de Nanociencia y Materiales de Aragón
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    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  2. 2 Instituto de Química Física Rocasolano
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    Instituto de Química Física Rocasolano

    Madrid, España

    ROR https://ror.org/03xk60j79

Revista:
Journal of the Chemical Society, Dalton Transactions

ISSN: 1472-7773

Año de publicación: 1989

Volumen: 10

Páginas: 1987-1992

Tipo: Artículo

DOI: 10.1039/DT9890001987 SCOPUS: 2-s2.0-37049068579 GOOGLE SCHOLAR

Otras publicaciones en: Journal of the Chemical Society, Dalton Transactions

Resumen

The tri-μ-hydroxo-dirhodium complex [{(C5Me5)Rh}2(μ-OH)3] [ClO4] (1) reacts with the appropriate amount of Ph2P(S)H, in acetone, to give [{(C5Me5)Rh}2(μ-OH)n(μ-Ph 2PS)3-n] [ClO4] [n = O(2) or 1(3)]. Reaction of complex (1) with an equimolar amount of Ph2P(S)H, in methanol gave the di-μ-methoxo-μ-diphenylthiophosphinito complex [{(C5Me5)Rh}2(μ-OMe)(2 (μPh2PS)] [ClO4] (5). The mixed-bridged complex [{(C5Me5)Rh}2(μ-OMe)(μ-pz)(μ-Ph 2PS)] [ClO4] (6) (pz = pyrazolate) was obtained by addition of Ph2P(S)H to a methanolic solution of [{(C5Me5)Rh}2(μ-OH)(μ- pz)2]-[ClO4]. The complexes (5) and [{(C5Me5)Rh}2(μ-OH)(μ-Ph 2PS)2][ClO4] (3) react with HCl yielding the binuclear chloride compounds [{(C5Me5) Rh}2(μ-Cl)2(μ-Ph2PS)] [ClO4] (7) and [{(C5Me5)Rh}2(μ-Cl)(μ-Ph 2PS)2][ClO4] (9). The doubly homo-bridged complex [{(C5Me5)-Rh(ButNC)}2(μ-Ph 2PS)2][ClO4], (10) can be prepared from [(C5Me5) Rh(acac)(ButNC)][ClO4] (acac = acetylacetonate ion) and an equimolar amount of Ph2P(S)H. The mononuclear species [(C5Me5)Rh(acac)Cl] reacts with an equimolar amount of Ph2P(S)H in the presence of NaBPh4 giving the binuclear complex [{(C5Me5)Rh}2(μ-Cl)(μ-Ph 2PS)2] [BPh4] (11). Its n.m.r. spectra show the presence of two isomers. Reaction of [{(C5Me5)RhCl}2(μ-Cl)2] with Ph2P(S)H and KOH yields the mononuclear complex [(C5Me5)Rh(Ph2PS-P) (Ph2PS-PS)] (12). This compound is converted by sulphur-atom abstraction into [(C5Me5)Rh(Ph2PS-P) (Ph2PS2-SS)] (13). The X-ray structure analysis of [{(C5Me5)Rh}2(μ-Cl)2(μ-Ph 2PS)][BPh4] (8) is also reported: the crystals are triclinic, space group P1, and have been refined to R 0.035 and R′ 0.038. The rhodium-rhodium distance is 3.570 1(5) Å.