Komplexe mit Phosphor und Arsen als terminalen Liganden

Scheer, Manfred; Müller, Jan; Häser, Marco

doi:10.1002/ange.19961082110

Cited by 45 publications

(65 citation statements)

References 36 publications

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“…The reaction proceeds significantly faster with the tungsten complex. [231] The reaction of 71 with [M'(CO) 5 (thf)] (M' Cr, W) leads to structurally interesting homo-and heterobimetal complexes [232] and with [GaCl 3 ] 2 to form a GaÀP adduct [233] (Scheme 54). With LiAsPh(H) a compound of the type Scheme 54.…”

Section: Reviewsmentioning

confidence: 99%

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Highlights in the Renaissance of Amidometal Chemistry

Kempe¹

2000

Angewandte Chemie International Edition

271

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Turning a disadvantage to an advantage: The rather disappointing reactivity of the metal - nitrogen bond in comparison to the metal - carbon bond resulted in the neglect of amidometal chemistry after its heyday at the end of the 1960s and beginning of the 1970s. Today it is precisely this disadvantage which is being applied through the use of amido ligands to produce inert complex fragments with well-defined reaction centers. In this way the chemistry of the early transition metals has been markedly enriched, and interesting alternatives to the classically regarded cyclopentadienyl ligands are now available.

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Section: Reviewsmentioning

confidence: 99%

“…[232,234] The WÀAs distance is 2.2903 (11) . The [(TMSN 3 N)W] fragment cannot be used for the preparation of an antimonido or bismuthido complex since the steric demand of the TMSN 3 N ligand is too large to enable a substitution of the chloro ligand.…”

Section: Reviewsmentioning

confidence: 99%

Highlights in the Renaissance of Amidometal Chemistry

Kempe¹

2000

Angewandte Chemie International Edition

271

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“…While the metal-ligand multiple-bond chemistry of singleatom ligands to date has featured most prominently the terminal oxo and nitrido functional groups, [1] recent developments have added terminal carbide [2][3][4][5][6][7][8] and phosphide [9][10][11][12][13][14][15][16][17][18] (alternatively carbido, phosphido) functional groups to the list of such available units. Terminal arsenic complexes were added to this list through the independent contributions of Schrock and Scheer.…”

Section: Introductionmentioning

confidence: 99%

“…Terminal arsenic complexes were added to this list through the independent contributions of Schrock and Scheer. [9,14] The outer limit so far for triple bonds between trivalent Group 6 metal fragments and heavier Group 15 3 . [19] Introduced herein is the idea that terminal, single-atom ligands constitute an attractive platform for the synthetic building up of interesting or unusual ligands within the protective coordination sphere of a metal complex.…”

Section: Introductionmentioning

confidence: 99%

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Cummins

2006

Angew Chem Int Ed

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Anionic terminal one‐atom nitride, phosphide, and carbide complexes are excellent starting materials for the synthesis of ligands containing low‐coordinate phosphorus centers in the protecting coordination sphere of the metal complex. Salt‐elimination reactions with chlorophosphanes lead to phosphaisocyanide, iminophosphinimide, and diorganophosphanylphosphinidene complexes in which the unusual phosphorus ligands are stabilized by coordination. X‐ray structure analyses and density‐functional calculations illuminate the bonding in these compounds.

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“…14 It could not be established whether 7 is the result of such an irreversible transfer reaction, or after an Sb-W bond formation an intermolecular Me 3 SiCl elimination is followed. The M-E-M system of such neutral complexes possesses a (1p u ) 4 (1p g ) 3 electron configuration with one unpaired electron. Therefore 7 is a mixed valent W(IV)/W(V) species.…”

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confidence: 99%

Antimony as a symmetrically bridged ligand in a novel neutral complex

Scheer¹,

Müller²,

Baum³

et al. 1998

Chem. Commun.

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[LWNSbNWL] 7 (L = N(CH 2 CH 2 N(Np)) 3 ; Np = CH 2 CMe 3 ) is prepared by treatment of [LWCl] 5 with LiSb(SiMe 3 ) 2 -(dme) n ; the ethylene complex [LWCl(C 2 H 4 )] 6 is a side product in the synthesis of 5; all complexes are structurally characterised.Complexes of the general formula [L n M·E] (E = P, As) with terminal ligands represent a new class of compounds. 6 While complex 5 dissolves well in toluene and is moderately soluble in pentane, compound 6 undergoes decomposition even in solvents of low polarity, resulting in the formation of an insoluble solid which could not be characterised. In the mass spectra of 5 and 6 the peaks for the molecular ions are observed. The 1 H NMR spectrum of 5 reveals broad signals at high and low field for the paramagnetic d 2 -tungsten complex. †The source of the ethylene in 6 is uncertain. It is possibly a result of a fragmentation of the tren ligand itself. Schrock and co-workers observed C-N bond cleavage of the ligand framework of a tren complex of tantalum, yielding a N-allyl unit. 7 Moreover, the low yields generally observed in the reactions of chlorotungsten(IV) complexes with tren ligands indicate various side reactions during the synthesis. 8 In the structure of the trigonal bipyramidal tungsten complex 5 the W-Cl and the W-N ax distances [2.389(2) and 2.179(5) Å] are only slightly shorter than the equivalent distances [2.399(2) and 2.182(6) Å] in the isostructural Me 3 Si substituted complex 4. ‡ In 6 (Fig.

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Komplexe mit Phosphor und Arsen als terminalen Liganden

Cited by 45 publications

References 36 publications

Highlights in the Renaissance of Amidometal Chemistry

Highlights in the Renaissance of Amidometal Chemistry

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Antimony as a symmetrically bridged ligand in a novel neutral complex

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