Dinuclear and diamagnetic zirconium(III) derivatives without Zr-Zr bond. Synthesis and x-ray structure of {Cp2Zr[.mu.-P(CH3)2]}2 and (Cp2Zr)2(.mu.-Cl)[.mu.-P(CH3)2]

Chiang, M. Y.; Gambarotta, Sandro; Vanbolhuis, F

doi:10.1021/om00098a026

Cited by 26 publications

(9 citation statements)

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“…In contrast to those found for 1, the P-Ti-P and Ti-P-Ti' angles in [Cp2Ti(pPMe2)]2 were found to average 83.3(1) and 96.5(1)", respectively. In the analogous Zr complex (18) [Cp2Zr(pPMe2)],, the P-Zr-P angle is 93.8(1)" while the Zr-P-Zr angle is 86.3(1)". The differences in the angles about the respective M2P2 cores give rise to differing metalmetal distances.…”

Section: Structural Study Ofmentioning

confidence: 99%

“…Furthermore, variations in the magnetic properties of the resultant metallocene-phosphide species appear to depend on how the low-valent precursor was generated. This confusion spurred recent structural studies of the complexes [Cp2M(p-PMe2)I2 (M = Ti ( 17), Zr ( 18)) in which the dimeric structure originally proposed by Issleib and Hackert was confirmed. In this report, we describe the structure and magnetic properties of the dimeric species [Cp2M(pPEt2)12 (M = Ti, 1; Zr, 2).…”

Section: Introductionmentioning

confidence: 99%

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Structure and magnetic properties of [Cp₂M(μ-PEt₂)]₂ (M = Ti, Zr)

Dick¹,

Stephan²

1991

Can. J. Chem.

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. Can. J. Chem. 69, 1 146 (1991). The complex ]2 (1) crystallizes in the monoclinic space group P2'/n with a = 16.591(3) A, b = 8.662 (2) A, c = 37.407(2) 1, P = 102.40(1)", Z = 8, and V = 5250(2) A'. The Ti2P2 core of the dimeric complex is planar and the angles at Ti and P are close to 90". The Ti.. .Ti separations were found to be 3.732(1) and 3.706(1) A in the two independent molecules in the unit cell. Bulk magnetic susceptibility measurements on solid 1 show that the species is diamagnetic over the range 5-340 K. The coupling constant for the antiferromagnetic interaction between the Ti centers of 1 is found to be at least -300 cm-'. Extended Hiickel Molecular Orbital calculations suggest that mixing of the frontier l a l orbitals of the Cp2Ti fragments with the p orbitals of the phosphide fragments affords a mechanism for super-exchange through the ligands. In THF solution, variable temperature 'H, and 3 '~{ '~) NMR and EPR spectra for 1 are consistent with the generation of the paramagnetic monomeric species Cp2TiPEt2, 3. As well, the data suggest thermal populations of the paramagnetic triplet state of the dimer may occur to a small extent at 340 K. In contrast, the analogous Zr dimer 2 shows no evidence of dissociation or of thermal population of the triplet state at temperatures to 340 K.Key words: titanium phosphides, structures, magnetic properties. IntroductionAs part of a continuing interest in early-late heterobimetallic (ELHB) complexes (1-1 1) we and others have recently described a route to monophosphido-bridged, ELHB species employing the Ti(II1) or Zr(II1) phosphido species [Cp2M(p-PR2:)I2 as precursors. While the chemistry of the derived ELHB complexes is a subject of ongoing investigations, further development in synthetic strategies to such complexes hinges on a thorough understanding of early metal phosphides.The preparation of the first zironocene(1V) diphosphide species (a) was first reported by Ellerman and Poersch in 1967 (12). However, it was not until the report of Baker et al. in 1983 (13), that a complete spectroscopic and structural study of metallocene(1V) diphosphides of the form (b), was presented.The related Ti(II1) and Zr(II1) phosphide species were first synthesized in 1966 by Issleib and Hackert (14). Subsequent spectroscopic studies suggested several species were formed in the reactions of phosphides with metallocene dihalides (16, 17).The nature of these ill-characterized species was dependent on the mode of preparation, nature of the phosphide substituents, and temperature of reaction. Furthermore, variations in the magnetic properties of the resultant metallocene-phosphide species appear to depend on how the low-valent precursor was generated. This confusion spurred recent structural studies of the complexes [Cp2M(p-PMe2)I2 (M = Ti ( 17), Zr ( 18)) in which the dimeric structure originally proposed by Issleib and Hackert was confirmed. In this report, we describe the structure and magnetic properties of the dimeric species [Cp2M(pPEt2)12 (M = Ti, 1; Zr, 2). The mag...

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Section: Structural Study Ofmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structure and magnetic properties of [Cp₂M(μ-PEt₂)]₂ (M = Ti, Zr)

Dick¹,

Stephan²

1991

Can. J. Chem.

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“…Proton NMR spectra show broad signals in a spectral window between 2 and 15 ppm. [24] The sterically more encumbered Zr III dimer [{(Me 3 Si) 2 C 5 H 3 } 2 Zr(μ-Cl)] 2 exhibits a 3.90 Å Zr···Zr distance and is paramagnetic. Three zirconium(III) atoms closely approximate an equilateral triangle with three Zr···Zr distances differing by less than 1 %.…”

Section: Resultsmentioning

confidence: 99%

Cyclononatetraenyl‐Indenyl Transformation and a Zirconium(III) Trimer from Bulky Alkylcyclopentadienylzirconium Chlorides

et al. 2013

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Keywords: Sandwich complexes / Trinuclear complexes / Titanium / Zirconium / Hafnium / Cyclopentadienyl ligandsStructure determinations of the known titanium, zirconium, and hafnium trichloro-di(tert-butyl)cyclopentadienyl complexes [CpЈЈMCl 3 ] {CpЈЈ = η 5 -C 5 H 3 tBu 2 , M = Zr (2), Ti (3), Hf (4)} on crystals obtained by sublimation show monomeric molecules in the solid state. Unlike the racemic di(tert-butyl)-(trimethylsilyl)cyclopentadienylzirconium trichloride 5, the 2,3-diisopropyl-1,4-dimethylcyclopentadienylzirconium trichloride 7 is not a monomer according to its low volatility and the presence of two similar sets of signals in the NMR [a]5694 spectra. Reactions of 2 or its CpЈЈЈ analogue [(η 5 -C 5 H 2 tBu 3 -1,2,4)ZrCl 3 ] (1) with potassium cyclononatetraenide did not afford the desired cyclononatetraenyl complexes [CpЈЈЈ (C 9 H 9 )ZrCl 2 ] or its CpЈЈ analogue, but the indenyl complexes [CpЈЈЈ(C 9 H 7 )ZrCl 2 ] (8) and [CpЈЈ(C 9 H 7 )ZrCl 2 ] (9). By reduction of the starting compound 1 with potassium a dark red, paramagnetic zirconium(III) complex was obtained and characterized as the cyclic trimer 10 with almost equal Zr···Zr distances of 3.384 Å.such as [CpTi(η 8 -C 8 H 8 )], [1][2][3] zirconium should be able to form cyclononatetraenyl sandwich complexes of the [CpZr(η 9 -C 9 H 9 )] type.The half sandwich complexes trichloro-1,2,4-tri(tert-butyl)cyclopentadienylzirconium (1) [4] and its 1,3-di(tert-butyl)cyclopentadienyl derivative 2 [5] were chosen as starting compounds for an investigation on the feasibility of cyclononatetraenylzirconium sandwich complexes.

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“…[5][6][7] Alternatively, derivatives of A with small organic groups at phosphorus are also formed by oxidative addition of tetraorgano-substituted diphosphanes onto the Zr(+2) centers of two zirconocene molecules, generated in situ by reduction of [Cp 2 ZrCl 2 ] with elemental Mg (Scheme 1). [8] The preference of other zirconocene derivatives to undergo redox processes [Zr(+4) Ǟ Zr(+3)] toward primary and secondary phosphanes is also distinctive for related zirconocene hydrido complexes. Thus, reaction of [Cp 2 Zr(H) Cl] (Schwartz reagent) with primary phosphanes RPH 2 affords in several ligand-exchange and redox processes AЈ, zirconocene dichloride and the respective diphosphane R 2 P 2 H 2 (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

From Dinuclear Zirconium(+3)‐Phosphido Complexes {[Cp₂ZrP(H)R]₂} to the First Neutral Zirconocene–Phosphinidene Dimers [(Cp₂ZrPR)₂] by P–H Dehydrogenation

2005

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The syntheses and structures of the new zirconium(+3) silylphosphanido complexes {[Cp 2 ZrP(H)R] 2 } 1a {Cp = η 5 -C 5 H 5 ; R = SiMe 2 C(iPr)Me 2 }, 1b (R = SiiPr 3 ), and 1c (R = SiF(tBu) (2,4,6-iPr 3 C 6 H 2 ) are reported. The latter are easily accessible by the reaction of the lithium salts of the corresponding primary silylphosphanes with the Schwartz reagent [Cp 2 Zr(H) Cl] in THF at -70°C. They can be isolated in the form of diamagnetic red-black crystals in 68-85 % yield. The central structural motif of the complexes consists of planar (1a, 1b) and slightly puckered Zr 2 P 2 rings (1c), and contains two d 1 -Zr(+3) centers, which are antiferromagnetically coupled (super exchange, through-bond interaction) although the transannular Zr-Zr separation is around 360 pm. Thus, the compounds have a biradicaloid electronic structure. Heating of solutions of 1a-c in toluene in the presence of Pd/C or [(Ph 3 P) 2 Pt(C 2 H 4 )] results in catalytic dehydrogenation of the P-H bonds, affording the first neutral zirconocene-phosphinidene

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Dinuclear and diamagnetic zirconium(III) derivatives without Zr-Zr bond. Synthesis and x-ray structure of {Cp2Zr[.mu.-P(CH3)2]}2 and (Cp2Zr)2(.mu.-Cl)[.mu.-P(CH3)2]

Cited by 26 publications

References 2 publications

Structure and magnetic properties of [Cp₂M(μ-PEt₂)]₂ (M = Ti, Zr)

Structure and magnetic properties of [Cp₂M(μ-PEt₂)]₂ (M = Ti, Zr)

Cyclononatetraenyl‐Indenyl Transformation and a Zirconium(III) Trimer from Bulky Alkylcyclopentadienylzirconium Chlorides

From Dinuclear Zirconium(+3)‐Phosphido Complexes {[Cp₂ZrP(H)R]₂} to the First Neutral Zirconocene–Phosphinidene Dimers [(Cp₂ZrPR)₂] by P–H Dehydrogenation

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Dinuclear and diamagnetic zirconium(III) derivatives without Zr-Zr bond. Synthesis and x-ray structure of {Cp2Zr[.mu.-P(CH3)2]}2 and (Cp2Zr)2(.mu.-Cl)[.mu.-P(CH3)2]

Cited by 26 publications

References 2 publications

Structure and magnetic properties of [Cp2M(μ-PEt2)]2 (M = Ti, Zr)

Structure and magnetic properties of [Cp2M(μ-PEt2)]2 (M = Ti, Zr)

Cyclononatetraenyl‐Indenyl Transformation and a Zirconium(III) Trimer from Bulky Alkylcyclopentadienylzirconium Chlorides

From Dinuclear Zirconium(+3)‐Phosphido Complexes {[Cp2ZrP(H)R]2} to the First Neutral Zirconocene–Phosphinidene Dimers [(Cp2ZrPR)2] by P–H Dehydrogenation

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Structure and magnetic properties of [Cp₂M(μ-PEt₂)]₂ (M = Ti, Zr)

Structure and magnetic properties of [Cp₂M(μ-PEt₂)]₂ (M = Ti, Zr)

From Dinuclear Zirconium(+3)‐Phosphido Complexes {[Cp₂ZrP(H)R]₂} to the First Neutral Zirconocene–Phosphinidene Dimers [(Cp₂ZrPR)₂] by P–H Dehydrogenation