Crystal and molecular structure of dinitrosyl-bis(triphenylphosphine)ruthenium-hemibenzene, Ru(NO)2(P(C6H5)3)2.1/2C6H6

Gaughan, Arthur P.; Corden, Brian J.; Eisenberg, Richard; Ibers, James A.

doi:10.1021/ic50134a005

Cited by 44 publications

(14 citation statements)

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“…Until quite recently, non-macrocyclic, four-coordinate ruthenium complexes were relatively rare. Tetrahedral geometry is most typical, but Wilkinson reported a square-planar bis(imido) ruthenium complex in 1992, and Caulton, Werner, and others have isolated several square-planar ruthenium complexes, including a 14e − (amido)(bisphosphine) complex that exhibits a high-spin ground state. ,, The paucity of square-planar Ru(0) complexes is somewhat surprising, as isoelectronic 16e − , d 8 Rh(I) and Pt(II) species are extremely common. However, such species have been proposed as reaction intermediates or generated as a short-lived transient species through flash photolysis and matrix isolation. , …”

Section: Discussionmentioning

confidence: 99%

Low-Valent Ruthenium Complexes of the Non-innocent 2,6-Bis(imino)pyridine Ligand

et al. 2010

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A series of low-valent ruthenium complexes bearing 2,6-bis(imino)pyridyl ("[N 3 ]") ligands has been synthesized and characterized. Reduction of [N 3 ) with hydridosilanes in an arene solvent such as toluene yields new 18eη 6 -arene complexes [κ 2 -N 3 ]Ru(η 6 -MeC 6 H 5 ), 2a,b,c, in which the [N 3 ] ligand is bidentate and only one imine group is coordinated to the metal. The arene ligand can be displaced with dinitrogen in non-arene solvents to yield the binuclear, four-coordinate, formally Ru(0) complexes {[N 3 ]Ru} 2 (μ-N 2 ), 3a,b,c. Pyrophoric complex 3c is a rare example of a structurally characterized Ru(0) dinitrogen complex. Treatment of low-valent complexes 2 or 3 with donor ligands generates five-coordinate complexes [N 3 xyl ]RuL 1,2 (L 1,2 =C 2 H 4 , 4a; L 1,2 =PMe 3 , 5a; L 1,2 =CO, 6a; L 1 =PMe 3 , L 2 =CO, 7a). Complexes 2a, 3c, 5a, 6a, and 7a are diamagnetic and have been structurally characterized by single-crystal X-ray diffraction methods. New six-coordinate Ru(II) complexes [N 3 xyl ]RuCl 2 (L) (L=PMe 3 , CO) were also isolated and structurally characterized. The infrared data, observed geometrical parameters, and reactivity patterns of the formally Ru(0) centers suggest varying degrees of electron delocalization to the "non-innocent" bis(imino)pyridyl, but probably not to the extent implied by the valence tautomeric [N 3 ] 2-/Ru(II) canonical form. Although the [N 3 ] -/Ru(I) representation may portray the electron distribution more accurately than "Ru(0)", the inherent odd electron counts on both ligand and metal;and requisite antiferromagnetic coupling;provides little in the way of "useful" distinctions or predictive value for the low-valent [N 3 ]Ru(L) 2 complexes with strong-field co-ligands such as CO and PMe 3. These five-coordinate adducts seem to be adequately described as Ru(0) complexes of the neutral [N 3 ] ligand. However, "non-innocent" valence tautomeric canonical forms such as [N 3 ] -/Ru þ may be more applicable to the four-coordinate dinitrogen complexes {[N 3 ]Ru} 2 (μ-N 2 ).

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Section: Discussionmentioning

confidence: 99%

Low-Valent Ruthenium Complexes of the Non-innocent 2,6-Bis(imino)pyridine Ligand

et al. 2010

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“…Under CO, two reactions can cause relatively slow release of PhCH=NOH and PhCN, respectively (7) and (8). Subsequent denitrosylation under C O will presumably follow according to reactions ( 9 + PhCN (12) The occurrence of PhCONH,, PhCHO, and PhCH,OH in the organic reaction products can be rationalised as arising from (metal-assisted) hydrolysis of PhCN, PhCH=NOH, and PhCH,Br.…”

Section: Discussionmentioning

confidence: 99%

Formation of N–C bonds via alkylation of transition metal nitrosyls. Reaction of ruthenium and other transition metal nitrosyls with benzyl bromide

McCleverty¹,

Ninnes²,

Wolochowicz³

1986

J. Chem. Soc., Dalton Trans.

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PhCHO, but in amounts smaller than those obtained under CO. In the absence of a metal, NO gas reacts with benzyl bromide in refluxing toluene to give PhCH,NO, (major product, 45%) and small amounts of PhCN, PhCHO, and PhCH,OH. Reaction of [Ru(NO),(PPh,),] with Ph'CH,CI and other alkyl b r o m i d es, a n d of [ R u ( N 0) , ( P h, P C H , C H , P P h , ) 3 , [ R u ( N 0 ) 1{ P ( 0 P h ) ,},I , [ C o ( N 0) { P ( 0 Et ) ,},I , [Rh(NO) (PPh,),], and [RhCI,(NO)(PPh,),] with PhCH,Br are briefly discussed.

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“…The N-M-N and M-N-O angles in fourcoordinate transition metal nitrosyls provide some evidence as to whether these can be regarded as NO + , NO or NO-complexes. Shortly after we had completed the determination of the structure of dinitrosylbis(triphcnylphosphine)ruthcnium, Gaughan, Corden, Eisenberg & Ibers (1974) reported a crystal structure in which four molecules of the same compound crystallize with two molecules of benzene in the monoclinic unit cell, with different packing and cell dimensions from the modification reported here. We thought that it would be of interest to compare the two independent determinations, especially since some parameters -e.g.…”

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confidence: 86%

Dinitrosylbis(triphenylphosphine)ruthenium

Bhaduri¹,

Sheldrick²

1975

Acta Crystallogr Sect B

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Ru(NO)2[P(C6Hs)3]z, monoclinic, P21/n, a= 9-96 (1), b=37.01 (2), c=9.31 (1)/~, fl=111.44 (3) °, Z = 4, Dx = 1.425, V= 3194/~3, F(000) = 662,/z(Mo K~) =5-28 cm -1. The structure has been refined by fullmatrix least-squares calculations to Rw = 0.0485 for 927 unique observed reflexions. There is a distorted tetrahedral coordination about ruthenium, with mean bond lengths and angles" Ru-P, 2.339 (7); Ru-N, 1.72 (3); N-O, 1.22 (2)/~; P-Ru-P, 105.5 (3); N-Ru-N, 139.9 (8) ° . Ru-N-O angles are 168.0 (1.6) and 174.7 (1.7) °. Apart from the conformation of the triphenylphosphine groups the molecular structure is similar to that found in crystals of Ru(NO)2[P(C6Hs)3]2 • ½C6H6.

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Crystal and molecular structure of dinitrosyl-bis(triphenylphosphine)ruthenium-hemibenzene, Ru(NO)2(P(C6H5)3)2.1/2C6H6

Cited by 44 publications

References 20 publications

Low-Valent Ruthenium Complexes of the Non-innocent 2,6-Bis(imino)pyridine Ligand

Low-Valent Ruthenium Complexes of the Non-innocent 2,6-Bis(imino)pyridine Ligand

Formation of N–C bonds via alkylation of transition metal nitrosyls. Reaction of ruthenium and other transition metal nitrosyls with benzyl bromide

Dinitrosylbis(triphenylphosphine)ruthenium

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