TY - JOUR
T1 - Reactions of [Os3(μ-H)2(CO)10] with organic azides
T2 - Structural characterization of [Os3(μ-H)(CO)10(μ-HN3Ph)] and [Os3(μ-H)2(CO)9(μ3-NPh)]
AU - Burgess, Kevin
AU - Johnson, Brian F.G.
AU - Lewis, Jack
AU - Raithby, Paul R.
PY - 1982
Y1 - 1982
N2 - The unsaturated cluster [Os3(μ-H)2(CO)10] reacts with azides N3R [R = Ph (1), Bun (2), CH2Ph (3), cyclo-C6H11 (4), or CPhCH2 (5)] to give complexes with the general formula [Os3(μ-H)(CO)10(HN3R)]. The structure of complex (1) has been established by an X-ray analysis, and shown to contain an equilateral Os3 triangle one edge of which is bridged by the HN3Ph group. This complex crystallises in the monoclinic space group P21/c with a = 9.665(3), b = 8.823(4), c = 25.571(14) Å, β = 100.17(4)°, and Z = 4. This structure was solved by a combination of direct methods and Fourier-difference techniques and refined by blocked-cascade least squares to R = 0.042 for 3 155 observed intensities. At 85 °C in 1,2-dimethoxyethane the complexes (1)-(4) liberate a N2 and a CO molecule to give complexes with the general formula [Os3(μ-H)2(CO)9(μ3-NR)] [R = Ph (6), Bun (7), CH2Ph (8), or cyclo-C6H11 (9)]. The structure of complex (6) contains an isosceles triangle of Os atoms which is capped by the N atom of the NPh group. This complex also crystallises in space group P21/c with a = 11.630(4), b = 9.217(4), c = 18.527(7) Å, β = 99.71(2)°, and Z = 4. The structure was solved and refined, by the same techniques as for complex (1), to R = 0.033 for 2 861 observed intensities. Thermolysis of the azido-1 -phenylethene adduct (5) under the same conditions, however, gave [Os3(μ-H)(CO)10(μ-NCMePh)] (10) presumably by rapid tautomerism after loss of N2. Azides with an electron-withdrawing substituent adjacent to the azido-function evolved N2 when reacted with [Os3(μ-H)2(CO)10] to give clusters of the type [Os3(μ-H)(CO)10(μ-NHR)] [R = PO(OPh)2 (11) or 2-(6-CINC5H3) (12)] or products which are, apparently, formed by rearrangement of this system, i.e. [Os3(μ-H)(CO)10(NHCOPh)] (14) (from phenacyl azide) and [Os3(μ-H)(CO)10(2-NHCN2HC6H 4)] (15) (from 2-azidobenzimidazole).
AB - The unsaturated cluster [Os3(μ-H)2(CO)10] reacts with azides N3R [R = Ph (1), Bun (2), CH2Ph (3), cyclo-C6H11 (4), or CPhCH2 (5)] to give complexes with the general formula [Os3(μ-H)(CO)10(HN3R)]. The structure of complex (1) has been established by an X-ray analysis, and shown to contain an equilateral Os3 triangle one edge of which is bridged by the HN3Ph group. This complex crystallises in the monoclinic space group P21/c with a = 9.665(3), b = 8.823(4), c = 25.571(14) Å, β = 100.17(4)°, and Z = 4. This structure was solved by a combination of direct methods and Fourier-difference techniques and refined by blocked-cascade least squares to R = 0.042 for 3 155 observed intensities. At 85 °C in 1,2-dimethoxyethane the complexes (1)-(4) liberate a N2 and a CO molecule to give complexes with the general formula [Os3(μ-H)2(CO)9(μ3-NR)] [R = Ph (6), Bun (7), CH2Ph (8), or cyclo-C6H11 (9)]. The structure of complex (6) contains an isosceles triangle of Os atoms which is capped by the N atom of the NPh group. This complex also crystallises in space group P21/c with a = 11.630(4), b = 9.217(4), c = 18.527(7) Å, β = 99.71(2)°, and Z = 4. The structure was solved and refined, by the same techniques as for complex (1), to R = 0.033 for 2 861 observed intensities. Thermolysis of the azido-1 -phenylethene adduct (5) under the same conditions, however, gave [Os3(μ-H)(CO)10(μ-NCMePh)] (10) presumably by rapid tautomerism after loss of N2. Azides with an electron-withdrawing substituent adjacent to the azido-function evolved N2 when reacted with [Os3(μ-H)2(CO)10] to give clusters of the type [Os3(μ-H)(CO)10(μ-NHR)] [R = PO(OPh)2 (11) or 2-(6-CINC5H3) (12)] or products which are, apparently, formed by rearrangement of this system, i.e. [Os3(μ-H)(CO)10(NHCOPh)] (14) (from phenacyl azide) and [Os3(μ-H)(CO)10(2-NHCN2HC6H 4)] (15) (from 2-azidobenzimidazole).
UR - https://www.scopus.com/pages/publications/37049113537
U2 - 10.1039/DT9820002085
DO - 10.1039/DT9820002085
M3 - Article
AN - SCOPUS:37049113537
SN - 1472-7773
SP - 2085
EP - 2092
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 10
ER -