“…This complex consists of an open triangular cluster of three Os(CO) 3 units with triply-bridging phenylimido and sulfido groups on opposite sites of the Os 3 triangle. Compound 1 is structurally similar to Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S), Ru 3 (CO) 9 (μ 3 -NPh)(μ 3 -S), Fe 3 (CO) 9 (μ 3 -NTol)(μ 3 -S), M 3 (CO) 9 (μ 3 -NPh) 2 (M = Fe, Ru 19 ), and M 3 (CO) 9 (μ 3 -S) 2 (M = Fe, Ru, Os 22 ), which contain 50 cluster valence electrons and require only two metal−metal bonds to satisfy the 18-electron rule on each metal atom. 3 ORTEP diagram of Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ).…”
Reaction of Os(3)(CO)(12) with thionylaniline (PhN=S=O) in refluxing methylcyclohexane produces Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S) (1) in good yield. When Os(3)(CO)(10)(NCMe)(2) is treated with PhN=S=O at room temperature, compound 1 and Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S) (2) result. Compound 1 reacts with trimethylamine oxide in the presence of acetonitrile to give Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S) (3). Compounds 1-3 were characterized by mass, IR, and NMR spectroscopies, and their structures were determined by single-crystal X-ray diffraction. Crystal data for 1: monoclinic (C2/c), a = 16.603(7) Å, b = 8.679(4) Å, c = 29.009(6) Å, beta = 102.08(2) degrees, Z = 8, R (R(w)) = 0.036 (0.039). Crystal data for 2: triclinic (P&onemacr;), a = 9.723(4) Å, b = 15.704(4) Å, c = 18.455(7) Å, alpha = 113.17(3) degrees, beta = 102.48(3) degrees, gamma = 89.97(3) degrees, Z = 4, R (R(w)) = 0.030 (0.026). Crystal data for 3: monoclinic (P2(1)/n), a = 18.792(3) Å, b = 8.856(3) Å, c = 26.210(9) Å, beta = 93.72(2) degrees, Z = 8, R (R(w)) = 0.066 (0.063).
“…This complex consists of an open triangular cluster of three Os(CO) 3 units with triply-bridging phenylimido and sulfido groups on opposite sites of the Os 3 triangle. Compound 1 is structurally similar to Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S), Ru 3 (CO) 9 (μ 3 -NPh)(μ 3 -S), Fe 3 (CO) 9 (μ 3 -NTol)(μ 3 -S), M 3 (CO) 9 (μ 3 -NPh) 2 (M = Fe, Ru 19 ), and M 3 (CO) 9 (μ 3 -S) 2 (M = Fe, Ru, Os 22 ), which contain 50 cluster valence electrons and require only two metal−metal bonds to satisfy the 18-electron rule on each metal atom. 3 ORTEP diagram of Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ).…”
Reaction of Os(3)(CO)(12) with thionylaniline (PhN=S=O) in refluxing methylcyclohexane produces Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S) (1) in good yield. When Os(3)(CO)(10)(NCMe)(2) is treated with PhN=S=O at room temperature, compound 1 and Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S) (2) result. Compound 1 reacts with trimethylamine oxide in the presence of acetonitrile to give Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S) (3). Compounds 1-3 were characterized by mass, IR, and NMR spectroscopies, and their structures were determined by single-crystal X-ray diffraction. Crystal data for 1: monoclinic (C2/c), a = 16.603(7) Å, b = 8.679(4) Å, c = 29.009(6) Å, beta = 102.08(2) degrees, Z = 8, R (R(w)) = 0.036 (0.039). Crystal data for 2: triclinic (P&onemacr;), a = 9.723(4) Å, b = 15.704(4) Å, c = 18.455(7) Å, alpha = 113.17(3) degrees, beta = 102.48(3) degrees, gamma = 89.97(3) degrees, Z = 4, R (R(w)) = 0.030 (0.026). Crystal data for 3: monoclinic (P2(1)/n), a = 18.792(3) Å, b = 8.856(3) Å, c = 26.210(9) Å, beta = 93.72(2) degrees, Z = 8, R (R(w)) = 0.066 (0.063).
“…It is, however, noteworthy that coordinated [ RNS(Me)NR] -may not only decompose in solution into NR and S=N fragments when bonded to electron rich metal atoms [6,7], but also when coordinated to highly electropositive metal atoms in high oxidation states.…”
Section: Ir Spectrum Of [Meai{rns(me)o)i and Rn(h)s(me)omentioning
confidence: 99%
“…The coordination of heteroolefins and the relation between their coordination to metal atoms and possible chemical activation has been studied in our laboratory mainly with compounds of cY-diimines RN=CH-CH=NR II-51, sulfur&mines RN=S=NR [6,7] and the analogous sulfinylanilines RN=S=O [7,8] and sulfines [9,10]. While for RNSNR and RNSO, ?I'-N, $-S and $-N=S coordination to metals has been observed, it has been demonstrated that chemical activation is favoured by initial q2-N=S coordination to low valent electron-rich transition metal atom centres [6,7].…”
Section: Introductionmentioning
confidence: 99%
“…While for RNSNR and RNSO, ?I'-N, $-S and $-N=S coordination to metals has been observed, it has been demonstrated that chemical activation is favoured by initial q2-N=S coordination to low valent electron-rich transition metal atom centres [6,7]. Most commonly the activated N=S bond is ruptured.…”
Reaction of sulfurdiimines RN=S=NR and the isoelectronic and structurallyThe dimeric complexes [Me,Al{RNS(Me)X}] (X = 0, NR) exist in two conformations which undergo intramolecular interconversion in the case of the sulfurdiimine compounds, and probably also for the sulfinylaniline derivatives. In the latter case intermolecular exchange via a monometic species also plays a role. This monomer may be observed in dilute solutions. While the sulfinylaniline compounds are stable in solution (CDCI,, pyridine), the sulfurdiimine compounds decompose slowly in CDCL, and rapidly in pyridine to produce diazoaryls, some RNH, and polymeric products. The alcoholysis of the sulfurdiimine-Al complexes also usually give similar products_ The possible roles of nitrene N-R and radical RNS-Me intermediates in the decompositions are discussed.
“…For RNSNR and RNSO it has been shown that chemical activation and subsequent N=S bond rupture is favoured by initial q2-N=S coo~~ation to low valent electron-rich transition metal atoms ]6,7], The RNS, S and NR fragments so formed may then be captured by formation of cluster complexes [6,7]. Chemical activation and conversion of RNSNR or -RNSO may also take place by addition of organolithium, organomagnesium [11,12] or organoaluminium compounds [5] to the N=S double bond.…”
Reaction of [Me2A1{RNS(Me)NRj], (R = 2,6-Me&H,) with t-BuOH affords N-methylthio-N'-(2,6-dimethylphenyl)-2,6-dimethyl-l,4-quinonediirnine in 67% yield. The X-ray structure of this compound shows that two confo~ational isomers are present in the solid. Temperature dependent 13C and 'H NMR measurements show that in solution these conformers exchange at a rate which is fast on the NMR time scale at +6O"C and slow at -60°C. From the coalescence point of two of the 13C resonances, the free energy of activation is estimated to be 13.7 + 1.0 kcallmol at 10°C. Possible processes for the exchange are discussed, and also a reaction scheme for the formation of the title compound is discussed.
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