Synthesis of Nitridoosmium(VI) Phosphine Complexes

Syntheses, electrochemistry, photophysics and photochemistry of nitridorhenium(V) diphosphine complexes and related nitridorhenium(V) organometallics; crystal structure of [ReVN(CCBut)2(PPh3)2]

“…The improved photophysical properties may also be related to the change of the geometry of the complex [ReNL,Cl]+ from a six-coordinate octahedron to a highly distorted pseudo-octahedron approaching five-co-ordination for [ReNL,(MeCN)12 + as a result of replacing the stronger (T donor, C1-by MeCN. Such changes in the co-ordination geometry have also been reported by Shapley et al,14 where the structure of [OsN(CH,-SiMe,),(dppe)(MeCN)]+ has been shown to be very similar to that of the five-co-ordinate alkylnitridoosmium(vr) complexes, with a pronounced distortion of the equatorial ligands away from the axial nitride and with a very weak MeCN-metal interaction.…”

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…[73][74][75][76] Organometallic Os(VI) nitrido species are also known. [77][78][79] Because of the stability and kinetic inertness of these osmium complexes, these complexes have been extensively used to explore the reactivity of the nitrido group. In general, Os(VI) nitrido complexes are electrophilic (though organometallic nitrides are nucleophillic) [79] and react with various nucleophiles to form products with new bonds to the nitride nitrogen atom (Scheme 8).…”

Metal–Ligand Multiple Bonds

“…[214] However, no ruthenium(VII) nitrido species has been reported up to date. A, [12] B, [215] C, [190] D, [216] E [217] F, [191] G, [218] H, [219] I, [28] J, [28] K, [220] L, [221] and M. [57] The first osmium nitrido complex was produced almost 175 years ago when Fritzsche and Struve [12] treated osmium(VIII) tetroxide with ammonia in 1847. However, it took another 50 years until Werner and Dinklage [215] [(Cl 4 )Ru VI N] -Az c SPY 157.0(7) [198] 1090 d [190] [(Br 4 )Ru VI [197] a Synthesis; Az: From corresponding azide; GP: Starting from [(Cl 4 )Ru VI N] -(Griffith and Pawson [190] ); EL: From elements in gas-phase; DA: By reaction with diphenyldiazomethane; OM: Reaction of oxo-metal complexes with an imine compound b Coordination Geometry; See Figure 1 [201] h Distorted square planar i From EXAFS fit j From RR k Average from 168.8(3) pm and 1.628(4) pm obtained by XRD and applying a split model for the nitride ligand because of considerable disorder regarding the nitrido ligand position.…”

“…[227] To an even greater extent than for the ruthenium congener, the nitrido tetrachloride anion [(Cl) 4 Os VI N]served as starting material for large number of complexes synthesized via ligand substitution reactions. [28,219,220,[228][229][230] Among those, the phosphine osmium(VI) complex [(dppe)(CH 2 SiMe 3 ) 2 (NCMe)Os VI N] + (Figure 1.10 D) that features an Os N bond distance of 163.8(5) pm, [216] as well as the square planar thiolate osmium(VI) complex [(S 2 C 6 H 4 ) 2 Os VI N] -(Figure 1.10 E), for which an Os N bond distance of 164(1) pm and an Os N stretching frequency of 1063 cm −1 was obtained. [217] The cationic complex [(hypyb)Os VI N] + (Figure 1.10, F) allows comparison of M N bond lengths and stretching frequencies with the complex of the lighter ruthenium congener [(hypyb)Ru VI N] + published in the same work.…”

“…Figure 1.10. Selection of experimentally known terminal osmium nitrido complexes:A,[12] B,[215] C,[190] D,[216] E[217] F,[191] G,[218] H,[219] I,[28] J,[28] K,[220] L,[221] and M [57]. …”