REACTIONS OF WITH ORGANIC AZIDES: STRUCTURAL CHARACTERIZATION OF 1,1,1,2,2,2,3,3,3,3-DECARBONYL-1,2-μ-HYDRIDO-1,2-μ-1'-PHENYLTRIANZNIDO(N1N3)-TRIANGULO-TRIOSMIUM AND 1,1,1,2,2,2,3,3,3,-NONACARBONYL-1,2;1,3-DI-μ-HYDRIDO-μ3-PHENYLIMIDO-TRIANGULO-TRIOSMIUM

Article abstract of DOI:10.1039/DT9820002085

The unsaturated cluster 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 X-ray analysis, and show to contain an equilateral Os3 triangle one edge of which is bridged by the HN3-Ph group.This complex crystallises in the monoclinic space group P2₁/c with a=9.665(3), b=8.823(4), c=25.571(14) Angstroem, β=100.17(4) deg, 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 3155 observed intensities.At 85 deg C in 1,2-dimethoxyethane the complexes ( 1 )-( 4 ) liberate a N2 and a CO molecule to give complexes with the general formula 3-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) Angstroem, β=99.71(2) deg, and Z=4.The structure was solved and refined, by the same techniques as for complex ( 1 ), to R=0.033 for 2861 observes 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-withdrawning 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-ClNC5H3) ( 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-NHCN2HC6H4) > ( 15 ) ( from 2-azidobenzimidazole ).

Full text of DOI:10.1039/DT9820002085

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