Formation of organonitrogen compounds via neutral ruthenium nitrosyl complexes

McCleverty, Jon A.; Ninnes, Clive W.; Wolochowicz, I.

doi:10.1039/c39760001061

Cited by 15 publications

(3 citation statements)

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“…The ruthenium complex [ Ru( CO) 2(NNPh)(PPh3)2] [PFs] (11) shows somewhat different behavior. The deprotonated complexes will slowly extract protons from freshly distilled methanol or ethanol; thus, the freshly prepared complexes must be rapidly filtered and removed from the reaction solvent since it contains small amounts of methanol or water.…”

Section: Discussionmentioning

confidence: 99%

Aryldiazo complexes. Syntheses and reactions of new complexes of osmium and ruthenium

Haymore¹,

Ibers²

1975

Inorg. Chem.

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Aryldiazo complexes, [M(CO)2(NNPh)(PPh3)2] [PF6] (M = Os, Ru; Ph = C6H5), have been prepared by allowing diazonium salts to react with M(CO)3(PPh3)2. Infrared spectra of the Ru complex suggest the presence of two isomers both in solution and in the solid state. These complexes react with a variety of coordinating anions (X-), to form MX(CO)2(NNPh)(PPh3)2. The osmium derivatives have v(NN) near 1455 cm-1, which is the lowest value yet reported for a nonbridging aryldiazo ligand. The first aryldiazo-hydrido complexes, MH(C0)2(NNPh)(PPh3)2 and MH(CO)(NNPh)(PPh3)2, were prepared by deprotonation of the respective phenyldiazene complexes, MH(CO)2(HNNPh)(PPh3)2+ and MH(CO)(HNNPh)(PPh3)3+. The compound OsCh(NNPh)(PPh3)2 has also been prepared. A large number of the foregoing complexes have been synthesized with selective 2H and 15N labels. Infrared and NMR spectra show MX(C0)2(NNPh)(PPh3)2 and the analogous hydrido complex to be pseudooctahedral with trans phosphine ligands, cis carbonyl ligands, and a doubly bent phenyldiazenido (NNPh-) ligand. Similarly, MH(CO)(NNPh)(PPh3)2 possesses a trigonal-bipyramidal geometry with trans phosphine ligands and an equatorial, singly bent phenyldiazoniumato (NNPh+) ligand. Isotopic substitution of the diazo ligand shows that v(NN) is often vibrationally coupled with phenyl vibrational modes and that two or three bands sometimes shift upon l5N substitution. Vibrational coupling is also observed in the higher energy region (1850-1900 cm-I) in the compound R U C I , ( N N C~D~) ( P P~~)~. The wide range in the values of u(NN), RuCh(NNPh)(PPh3)2 (I882 cm-I), vs. RuCI-(C0)2(NNPh)(PPh3)2 (I462 cm-I), indicates that the N-N stretching frequencies are sensitive to the electronic and steric environment of the diazo ligand. The aryldiazo complexes are compared with analogous, isoelectronic nitrosyl complexes of Os and Ru.been reported for all members of the Cr, Mn, Fe, Co, and Ni triads with the exception of Ni, Pd, and Tc.4>5 Part of the interest in aryldiazo and other diazo ligands has been generated by the close relationship of these ligands to dinitrogen and nitrosyl ligands. Recent work has shown that diazo ligands can be prepared from coordinated dinitrogen in Re, Mo, and W complexes.6 Furthermore, aryldiazo ligands resemble

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Section: Discussionmentioning

confidence: 99%

Aryldiazo complexes. Syntheses and reactions of new complexes of osmium and ruthenium

Haymore¹,

Ibers²

1975

Inorg. Chem.

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“…Although mechanistic studies have not been reported, it is suggested that the reaction proceeds via oxidative addition of benzyl halide to be cobaltate anion: "o=n; In a more recent study, the reactions of benzyl bromide with neutral nitrosyl complexes in hydrocarbon solvents have been examined. 78 Benzyl bromide is a particularly convenient substrate, since, if it is converted to PhCH2NO, it will readily tautomerize to PhCH=NOH, which is easily characterized. The most extensively investigated compound has been [Ru(NO)2-(PPh3)2], which is relatively stable In solution and is easily prepared.…”

Section: Formation Of N-c Bondsmentioning

confidence: 99%

Reactions of nitric oxide coordinated to transition metals

McCleverty¹

1979

Chem. Rev.

311

113

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“…The proposed formulation was confirmed by fortuitously obtained by reaction of [Re(CO) 4 Cl] 2 with an X-ray diffraction study (see later). K[HB(dmpz) 3 ] [12] .…”

Section: Introductionmentioning

confidence: 99%