Notizen: Osmium(II)-Olefinkomplexe

Winkhaus, G.; Singer, Hellmut; Kricke, Manfred

doi:10.1515/znb-1966-1126

Cited by 29 publications

(16 citation statements)

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“…[(C 6 H 6 )OsI 2 ] 2 : [28] 1.00 g of OsCl 3 ·3H 2 O, 2.0 mL of cyclohexa-1,3-diene and 1.2 g of I 2 was dissolved in the 50 mL of EtOH. The reaction mixture was refluxed with vigorous stirring for 12 h, cooled and a brown powder was filtered, washed with EtOH (10 mL) and Et 2 O (10 mL).…”

Section: Methodsmentioning

confidence: 99%

Redox and Lewis Acid Reactivity of Unsaturated Os^II

et al. 2010

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A synthesis of [(PNP)OsI] {PNP = (tBu2PCH2SiMe2)2N} permits evaluation of its reactivity, both Lewis acidity and reducing power (i.e., ability to be oxidized). It binds two molecules of PhCN, into trans sites, but only one of ethylene, and, upon binding of one N2, there is heterolytic splitting of one tBu C–H bond to put the proton on amide N and the carbon on Os, leaving divalent metal in [{PN(H)P*}Os(N2)(I)]. Two moles of H2 add, forming [{PN(H)P}OsH(H2)I], via H–H bond heterolysis. Thermolysis of [(PNP)OsI] gives the product of adding a tBu methyl C–H bond across the Os/N bond, and also net dehydrogenation of this intermediate, forming a carbene complex; the released H2 forms [(PNP)OsH2I], and the chemistry of [(PNP)Os] hydridohalides is described. Reaction with O2 occurs with no detectable intermediate, to completely split the O=O bond, and form trans‐[(PNP)Os(O)2I], a product of four electron redox change. Attempted two electron oxidation by oxygen atom transfer with pyridine N‐oxide or Me3NO or N2O surprisingly effect transposition of N from its silyl substituents onto the metal, and replace N by O, forming a nitride complex of a bis(silyl ether, phosphane) chelate whose oxygen fails to bind to Os. The product is thus four‐coordinate, tetrahedral [(POP)Os(N)I], with an Os/N triple bond.

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Section: Methodsmentioning

confidence: 99%

Redox and Lewis Acid Reactivity of Unsaturated Os^II

et al. 2010

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“…Ausgewahlte Bindungslangen (pm) und -winkel (") von 1 j (1 -X (1 1 179.2 (12) 83.8(4) 123.4 (9) 108.6(12) 106.9 (14) 107.9(14) 112.5 ( -'H-NMR (D20 rnit LEI): 6 = 8.08 (m, AryI-3,5-H), 7.33 (m, Aryl-2,6-H), 3.74 (m, H"), 2.7 -3.2 (m, Hp).…”

Section: (Q~-benzol)chloro(4-nitro-~-phenylalaninato)ruthenium(ii) (4c)mentioning

confidence: 99%

Chirale Halbsandwich‐Komplexe von Rhodium(III), Iridium(III), Iridium(I) und Ruthenium(II) mit α‐Aminosäure‐Anionen

Krämer¹,

Polborn²,

Wanjek³

et al. 1990

Chem. Ber.

122

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“…Ber. 115 (1982) Darstellung der Komplexe ArRuC12(CO) (8,9) [C&&uCI(L)(ac)]PF6 (10 -12): Zu 1.5 mmol C6H,RuC12(PR3) (PR, = PMe,, PMe2Ph, PPh,) in 10 ml Aceton wird bei Raumtemp. langsam eine Losung von Tab.…”

Section: Nameunclassified

Aromaten(phosphan)metall‐Komplexe, I. Die Vorstufen zur Synthese der Metall‐Basen ArM(PR₃)₂ und ArM(PR₃)L (M = Ru, Os)

Werner

1982

Chem. Ber.

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Die halogen‐verbrückten Verbindungen [ArRuX2]2 (AR = C6H6, p‐Cymol, C6Me6; X = Cl, und AR = C6H6; X = I) und [C6H6OsI2]2 reagieren mit Lewis‐Basen L wie z. B. CO, tertiären Phosphanen oder Trimethylphosphit zu den einkernigen Komplexen ArMX2(L) (1 – 9). Aus diesen erhält man (für AR = C6H6) mit AgPF6 in Aceton (ac) die Verbindungen [C6H6RuCl(L)(ac)]PF6 (10 – 12) und [(C6H6ML)2(μ‐X)2(PF6)2](C6H6ML)[2(μ‐X)2](PF6) 2 (13 – 20). Bei der Reaktion von [ArRuX2]2 und [C6H6OsI2]2 mit einem Überschuß an PR3 und NH4PF6 in Methanol entstehen die Komplexe [ArMX(PR3)2]PF6 (21 – 29). Die Synthese der analogen Verbindungen [ArMX(PR3)L]PF6 (30 – 39) gelingt durch Umsetzung von ArMX2(L) mit PR3 und NH4PF6 in Methanol. Die Osmium‐Komplexe [C6H6OsI(L)2]PF6 (40, 41) und [C6H6OsI(PR3)CO]PF6 (42, 43) werden aus [(C6H6OsL)2(μ‐I)2(PF6)2] und L bzw. aus C6H6OsI2(PR3) und CO in Gegenwart von AgPF6 dargestellt.

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Notizen: Osmium(II)-Olefinkomplexe

Cited by 29 publications

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Redox and Lewis Acid Reactivity of Unsaturated Os^II

Redox and Lewis Acid Reactivity of Unsaturated Os^II

Chirale Halbsandwich‐Komplexe von Rhodium(III), Iridium(III), Iridium(I) und Ruthenium(II) mit α‐Aminosäure‐Anionen

Aromaten(phosphan)metall‐Komplexe, I. Die Vorstufen zur Synthese der Metall‐Basen ArM(PR₃)₂ und ArM(PR₃)L (M = Ru, Os)

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Notizen: Osmium(II)-Olefinkomplexe

Cited by 29 publications

References 0 publications

Redox and Lewis Acid Reactivity of Unsaturated OsII

Redox and Lewis Acid Reactivity of Unsaturated OsII

Chirale Halbsandwich‐Komplexe von Rhodium(III), Iridium(III), Iridium(I) und Ruthenium(II) mit α‐Aminosäure‐Anionen

Aromaten(phosphan)metall‐Komplexe, I. Die Vorstufen zur Synthese der Metall‐Basen ArM(PR3)2 und ArM(PR3)L (M = Ru, Os)

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Redox and Lewis Acid Reactivity of Unsaturated Os^II

Redox and Lewis Acid Reactivity of Unsaturated Os^II

Aromaten(phosphan)metall‐Komplexe, I. Die Vorstufen zur Synthese der Metall‐Basen ArM(PR₃)₂ und ArM(PR₃)L (M = Ru, Os)