TY - JOUR

T1 - Rh(I) carbonyl carboxylato complexes

T2 - Spectral and structural characteristics. Some reactions of coordinated formate group

AU - Varshavskii, Yu S.

AU - Cherkasova, T. G.

AU - Podkorytov, I. S.

AU - Korlyukov, A. A.

AU - Khrustalev, V. N.

AU - Nikol'skii, A. B.

PY - 2005/2

Y1 - 2005/2

N2 - Complexes [Rh(μ-RCOO)(CO2)]2, where R = H, CH 3, CF3 (I, II, III, respectively) are synthesized by reacting anhydrous carboxylic acids with Rh(Acac)(CO2) crystals. In compounds I, II, III, and trans-Rh(RCOO)(PPh3)2(CO), where R = H, CH3, CF3 (IV, V, VI, respectively), ν(CO) and 1J(CRh) increase and δ13C decreases with the increasing electronegativity of R (CH3 < H < CF3). In the case complexes IV, V, and VI, the values of δ31P and 1J(PRh) decrease in the same order. Complexes I and V are studied by X-ray diffraction analysis. Intramolecular (2.946 Å) and intermolecular (3.127 Å) Rh-Rh distances in a columnar structure I are close, i.e., the structure contains infinite chains of metal atoms. Interaction of IV with chlorinated solvents results in trans-RhCl(PPh3)2(CO). When heated with an excess of PPh3 in propanol-2, compound IV transforms to HRh(PPh3)3(CO). The latter reaction was suggested as a basis of a new method that can be used to obtain HRh(PPh 3)3(CO).

AB - Complexes [Rh(μ-RCOO)(CO2)]2, where R = H, CH 3, CF3 (I, II, III, respectively) are synthesized by reacting anhydrous carboxylic acids with Rh(Acac)(CO2) crystals. In compounds I, II, III, and trans-Rh(RCOO)(PPh3)2(CO), where R = H, CH3, CF3 (IV, V, VI, respectively), ν(CO) and 1J(CRh) increase and δ13C decreases with the increasing electronegativity of R (CH3 < H < CF3). In the case complexes IV, V, and VI, the values of δ31P and 1J(PRh) decrease in the same order. Complexes I and V are studied by X-ray diffraction analysis. Intramolecular (2.946 Å) and intermolecular (3.127 Å) Rh-Rh distances in a columnar structure I are close, i.e., the structure contains infinite chains of metal atoms. Interaction of IV with chlorinated solvents results in trans-RhCl(PPh3)2(CO). When heated with an excess of PPh3 in propanol-2, compound IV transforms to HRh(PPh3)3(CO). The latter reaction was suggested as a basis of a new method that can be used to obtain HRh(PPh 3)3(CO).

UR - http://www.scopus.com/inward/record.url?scp=15244339509&partnerID=8YFLogxK

U2 - 10.1007/s11173-005-0008-3

DO - 10.1007/s11173-005-0008-3

M3 - Article

AN - SCOPUS:15244339509

VL - 31

SP - 121

EP - 131

JO - Russian Journal of Coordination Chemistry

JF - Russian Journal of Coordination Chemistry

SN - 1070-3284

IS - 2

ER -