Synthesis and reactivity of (.eta.5-C5H5)Os(N)(CH2SiMe3)2, the first cyclopentadienyl-nitrido transition-metal complex

Marshman, Robert W.; Shusta, Jeanine M.; Wilson, Scott R.; Shapley, Patricia A.

doi:10.1021/om00052a011

Cited by 40 publications

(29 citation statements)

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“…(Figure 3) shows the molecule to have the C s symmetry deduced from NMR spectra, but the monatomic ligand attached to Os has bond length too short for Os/O but appropriate for an Os/N triple bond. [21] The heteroatom in the pincer ligand does not coordinate to Os, but is 3.14 Å distant from it, consistent with a poorly nucleophilic bis(silyl ether) O atom. The molecule is thus [(POP)Os(N)I], containing four coordinate osmium, with a flattened tetrahedral coordination geometry.…”

Section: Reaction Of [(Pnp)osi] With Omentioning

confidence: 95%

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: Reaction Of [(Pnp)osi] With Omentioning

confidence: 95%

Redox and Lewis Acid Reactivity of Unsaturated Os^II

et al. 2010

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“…[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).…”

Section: Imido Complexes Of the Late Transition Metals 37mentioning

confidence: 99%

“…[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). [80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98] The nitrido group in these Os compounds does not display significant nucleophilicity.…”

Section: Imido Complexes Of the Late Transition Metals 37mentioning

confidence: 99%

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Berry

2009

Comments on Inorganic Chemistry

285

232

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Compounds that contain a late transition metal-nitrogen multiple bond represent important reactive intermediate species in many useful organic and inorganic transformations. In order to understand the role that these intermediates play in reactions, it is important to have a full understanding of their electronic structure. This paper reviews the known structural motifs that occur in late transition metal nitrido and imido compounds, and provides a correlation between geometric structure and electronic structure. Also, intermediate species that have been postulated but not yet isolated are discussed, as these compounds represent exciting targets for further efforts in synthetic inorganic chemistry.

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“…The ruthenium centers have a distorted square pyramidal geometry and are joined through the bridging hydroxyl ligands with equidistant Ru-OH bond distances. The Ru-Ru distance of 3.3407 (5) shows no metal-metal interaction. Bond distances and angles are shown in Table 2.…”

Section: Reactivity Of the Trialkyl Complexesmentioning

confidence: 96%

“…IR u ( N ) ( c H~i~e 3 ) *~Y )~l r B F~l ,5 Pyridinium tetrafluoroborate (O.OlOg, 0.062 mmol) was added to a solution of 1 (0.028 g, 0.062 mmol) in 5 mL CH2C12. After stirring for 16 h the orange solution was filtered through Celite, the CH,CI, removed under vacuum and the orange residue dissolved in diethyl ether.…”

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confidence: 99%

Synthesis and Reactivity of Nitridoruthenium(vi) Complexes of Weakly Coordinating Ligands

Shapley

Schwab

Wilson

1994

Journal of Coordination Chemistry

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Neutral, trialkylruthenium complexes Ru(N)R,L (R = CH,, CH,SiMe,; L = pyridine, 2,6-lutidine, 4-picoline, PMe,, CNCMe,) were prepared by the reaction of [Ru(N)R,]-salts with HBF4 and the ligand, L. The molecular ,structure of Ru(N)(CH,SiMe,,(py) was determined by X-ray diffraction. Crystals of Ru(N)(CH,SiMe, ,(py) are monoclinic in space group. P2,ln with a -14.551(5) A, b=9.113(4)& c = 19.801(5) a , a = y = 9 0 " , p = 109.27(2), 2 = 4 , R-0.032 and R,=0.039. The neutral dialkyl complex, Ru(N)R,CI, is in equilibrium with the dimer and adds a variety of neutral, two-electron ligands. Cationic complexes [Ru(N)R,L,][BF],] (R = CH,, CH,SiMe,;L = NCCH,, pyridine) were prepared by the reactions of Ru(N)R,L with HBF, and additional ligand. The addition of concentrated HN03(,,, to [Ru(NO)R,]-gave the nitrato complexes [Ru(N)R,(ONO,),]-. The complexes [Ru(N)R,L,][BF,] react with water to form the p-hydroxo dimers, {Ru(N)R,(p-OH)},. The molecular structure of {Ru(N)(CH),SiMe,),(pOH)} was determined by X-ray diffraction. Crystals of {Ru(N)(CH)]~S~M~,),(~-OH)} are monoclinic in space group P2,la with u -11.510(8) A, b=20.440(8) A, c=12.858(4) A, a = y = 9 0°, p=109.04, Z = 4 , R=0.027 and R,=0.029. The acetonitrile complex, [Ru(N)(CH,SiMe,),(NCMe),l[BF,], is a catalyst for the polymerization of ethylene.

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Synthesis and reactivity of (.eta.5-C5H5)Os(N)(CH2SiMe3)2, the first cyclopentadienyl-nitrido transition-metal complex

Cited by 40 publications

References 3 publications

Redox and Lewis Acid Reactivity of Unsaturated Os^II

Redox and Lewis Acid Reactivity of Unsaturated Os^II

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Synthesis and Reactivity of Nitridoruthenium(vi) Complexes of Weakly Coordinating Ligands

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Synthesis and reactivity of (.eta.5-C5H5)Os(N)(CH2SiMe3)2, the first cyclopentadienyl-nitrido transition-metal complex

Cited by 40 publications

References 3 publications

Redox and Lewis Acid Reactivity of Unsaturated OsII

Redox and Lewis Acid Reactivity of Unsaturated OsII

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Synthesis and Reactivity of Nitridoruthenium(vi) Complexes of Weakly Coordinating Ligands

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Redox and Lewis Acid Reactivity of Unsaturated Os^II

Redox and Lewis Acid Reactivity of Unsaturated Os^II