Transition-metal dialkylamides and disilylamides

Bradley, D. C.; Chisholm, Malcolm H.

doi:10.1021/ar50103a005

Cited by 198 publications

(104 citation statements)

References 71 publications

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“…The reaction between W 2 (NMe 2 ) 6 and excess PrtOH has been carried out in sealed vessels and the gaseous products have been analyzed. In addition to the expected dimethylamine, small quantities of molecular hydrogen have been detected.…”

Section: Resultsmentioning

confidence: 99%

“…The first step of the reaction, 2a, is an 2a W 2 (NMe 2 ) 6 + PriOH(excess) -W2(OPrt )6 + 6 HNMe 2 alcoholysis reaction and is common to all transition metal dimethylamides. 6 For molybdenum, the reaction stops here, yielding the well characterized compound Mo 2 (OPr 1 ) 6 (ME M). 3 For tungsten, the W 2 (OPr') 6 formed in 2a will be solvated either by HNMe 2 or, more likely, PriOH since the latter is present in excess.…”

Section: Resultsmentioning

confidence: 99%

“…Indeed, only the extremely bulky tert-butoxy ligand gave a simple dinuclear compound, W 2 (OBut) 6 , in the alcoholysis reaction 1, and this was not thermally stable. The reaction involving isopropanol and pyridine as solvent gave 6 (py) 2 which contained four coordinate tungsten atoms united by a triple bond. Tungsten showed a marked preference, relative to molybdenum, to increase its coordination number.…”

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confidence: 99%

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The tetradecaisopropoxydihydridotetratungsten story

Akiyama¹,

Chisholm²,

Cotton³

et al. 1981

J. Am. Chem. Soc.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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The tetradecaisopropoxydihydridotetratungsten story

Akiyama¹,

Chisholm²,

Cotton³

et al. 1981

J. Am. Chem. Soc.

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“…This conclusion is supported by the observation that unsubstituted 8-amidoquinoline complexes of Zn 2+ show a distorted tetrahedral coordination sphere, whereas Ni 2+ has a square-planar environment, which is characteristic for a low-spin d 8 system. [4] In contrast to the (6), Co (7)] are dimeric with bridging 8-amidoquinoline moieties. The 2:1 complexes of Mn and Fe, bis(8-amidoquinoline)-manganese(II) (8) and bis(8-amidoquinoline)iron(II) (9), form hexamers with wheel-like molecular structures consisting of metal-centered nitrogen octahedra interconnected by common N···N edges.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures, and Magnetic Properties of N‐Trialkylsilyl‐8‐amidoquinoline Complexes of Chromium, Manganese, Iron, and Cobalt as well as of Wheel‐Like Hexanuclear Iron(II) and Manganese(II) Bis(8‐amidoquinoline)

et al. 2010

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“…The low coordination number at one of the metal centers suggests that this metal may engage in further reactivity; indeed twoand three-coordinate complexes have special facility for activation and transformation of small molecules. [1,6] Metalmetal bonds are also reactive, and this combination of features is distinctive and promising with respect to smallmolecule reactions.…”

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confidence: 99%

Two‐Coordinate Transition‐Metal Centers With Metal–Metal Bonds

Holland

2011

Angew Chem Int Ed

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electron-deficient compounds · iron · low-coordinate metals · metal-metal interactions · xenophilic complexesThe most common coordination numbers for complexes of transition metals are four, five, and six. However, the use of very bulky supporting ligands can enable the isolation of complexes with low coordination numbers of three and even two.[1, 2] Scheme 1 shows some examples of supporting ligands that enforce two-coordination. [2,3] Because of the great steric protection of these supporting ligands, additional ligands and solvent can be prevented from bonding to the metal center. Two-coordinate complexes have been isolated primarily with the 3d transition metals, because of the small size of the metal and consequent ability to more easily block coordination of added donors. [2] A recent contribution from Power et al.[4] stands out by demonstrating novel two-coordinate complexes in which part of the steric protection comes not from an organic supporting ligand like those in Scheme 1 but instead from a second metal fragment that forms a metal-metal bond. Complexes of this type that have metal-metal bonds between metals of different character have been termed "xenophilic".[5] Such "strangerloving" complexes combine the properties of two different metal types, thus providing opportunities for new understanding of bonding and interesting combinations of reactivity modes.The new xenophilic complexes of the Power group come from the addition of K[CpFe ( Figure 1. The illustration shows that the ortho substituents of the aryl rings surround the two-coordinate metal center, thus blocking the formation of any third bond to Fe(1). The bulky substituents also hold the metals in near-linear geometries, with angles of 163.9(1)8 and 166.82(6)8 at Fe and Mn, respectively.The metal-metal distances in the complexes are very short: 2.3931(8) for FeÀFe, 2.4512(5) for FeÀMn, and 2.4887(5) for FeÀCr. The shortness of the bonds may be a Scheme 1. Bulky supporting ligands that have been used to stabilize two-coordinate complexes of the 3d transition metals. Mes = 2,4,6-Me 3 C 6 H 2 , Dipp = 2,6-iPr 2 C 6 H 3 .Scheme 2. Synthesis of metal complexes with two-coordinate metals stabilized by metal-metal dative bonds.

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Transition-metal dialkylamides and disilylamides

Cited by 198 publications

References 71 publications

The tetradecaisopropoxydihydridotetratungsten story

The tetradecaisopropoxydihydridotetratungsten story

Synthesis, Structures, and Magnetic Properties of N‐Trialkylsilyl‐8‐amidoquinoline Complexes of Chromium, Manganese, Iron, and Cobalt as well as of Wheel‐Like Hexanuclear Iron(II) and Manganese(II) Bis(8‐amidoquinoline)

Two‐Coordinate Transition‐Metal Centers With Metal–Metal Bonds

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