Synthesis, characterization, and X-ray crystal structures of W(VI) alkyl complexes with chelating diamide and imido co-ligands

Boncella, James M.; Wang, Shu-Yu S.; VanderLende, Daniel D.; Huff, R. Leigh; Abboud, Khalil A.; Vaughn, William M.

doi:10.1016/s0022-328x(96)06439-x

Cited by 41 publications

(29 citation statements)

References 21 publications

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“…The tungsten atom resides 0.717 Å above the plane defined by N(1), N(2), C(1), and C(4) (mean deviation is 0.001 Å). The W−C(1) and W−C(4) bond lengths (2.182(5), 2.183(5) Å, respectively) are within the range expected for W(VI)−C distances. , The W−N imido bond length is 1.736(4) Å and is consistent with a W−N triple bond. , The geometry about the N atoms of the [ o -(Me 3 SiN) 2 C 6 H 4 ] 2- ligand is planar as is observed in silylamines . The ligand is folded about the N−N vector which causes the SiMe 3 groups to be displaced above the basal plane.…”

Section: Resultssupporting

confidence: 60%

“…A comparison of the W−N amide bond lengths in 5 with the six coordinate dialkyl complex W(NPh)(CH 3 ) 2 [ o -(Me 3 SiN) 2 C 6 H 4 ](PMe 3 ) reveals that W−N(2) in 5 is 0.1 Å longer that the W−N amide bonds (both cis to the imido group) in W(NPh)(CH 3 ) 2 [ o -(Me 3 SiN) 2 C 6 H 4 ](PMe 3 ) …”

Section: Resultsmentioning

confidence: 99%

“…Toluene, pentane, and hexane were distilled from sodium. The compounds 1 and 2a,b,f,h,j were prepared as described previously . NMR solvents were stored over molecular sieves and were degassed prior to use.…”

Section: Methodsmentioning

confidence: 99%

“…Recent work , in our group has successfully used N , N ‘-bis (trimethylsilyl)- o -phenylenediamide, [ o -(Me 3 SiN) 2 C 6 H 4 ] 2- , TMS 2 pda, as an ancillary ligand for a variety of tungsten(VI) complexes. The facile synthesis of W(NPh)R 2 [ o -(Me 3 SiN) 2 C 6 H 4 ], 2(a − j) , from W(NPh)Cl 2 [ o -(Me 3 SiN) 2 C 6 H 4 ], 1 , (eq 1) for a wide range of alkyl groups has allowed us to begin to explore the chemistry of this class of d 0 dialkyl complexes.…”

Section: Introductionmentioning

confidence: 99%

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Metallacyclopentane Formation: A Deactivation Pathway for a Tungsten(VI) Alkylidene Complex in Olefin Metathesis Reactions

et al. 1998

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W(NPh)[o-(Me3SiN)2C6H4](CH2CMe3)2, 2h, is quantitatively converted to a new metallacyclopentane complex, W(CH2CH2CH2CH2)(NPh)[o-(Me3SiN)2C6H4], 4, upon the addition of ethylene at T > 70 °C. The complex W(CH2CH2CH2CH2)(NPh)[o-(Me3SiN)2C6H4], 4, was also formed by the transmetalation reaction of W(NPh)[o-(Me3SiN)2C6H4](Cl)2 with the corresponding Grignard reagent, BrMg(CH2)4MgBr, and also when W(NPh)[o-(Me3SiN)2C6H4](PMe3)(C(H)t-Bu), 3, reacts with ethylene. Mechanistic studies suggest that 2h and 3 react with ethylene through a common base-free alkylidene intermediate which undergoes metathesis with ethylene and then generates a W(IV) intermediate which is converted to 4 by coupling two molecules of ethylene. This reaction is a deactivation pathway when 3 is used as an olefin metathesis catalyst for terminal olefins because ethylene is generated during the reaction. The tungsten(IV) complex W(NPh)[o-(Me3SiN)2C6H4](PMe3)2(η2-C2H4), 5, was observed during the reaction between 3 and ethylene. Complex 5 can also be synthesized from the diethyl complex W(NPh)[o-(Me3SiN)2C6H4](CH2CH3)2, 2b, in the presence of PMe3. Addition of excess ethylene to 5 gives 4. The X-ray structure of 4 was determined.

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Section: Resultssupporting

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Metallacyclopentane Formation: A Deactivation Pathway for a Tungsten(VI) Alkylidene Complex in Olefin Metathesis Reactions

et al. 1998

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“…To our knowledge, only five examples of compounds with a coordinated phosphine trans with respect to an organoimido ligand have been structurally characterized for group 6. Four of them are tungsten complexes, namely, W(N-2,6- i Pr 2 C 6 H 3 )Cl 3 (dppe), W(NPh)(C⋮CPh) 2 (PhC⋮CPh)(PMe 3 ) 2 (Nielson and co-workers), and W(NPh)(R) 2 [(Me 3 SiN) 2 C 6 H 4 ](PMe 3 ) (R = Cl, Me) (Boncella and co-workers). The other one, recently reported by us, is the somewhat related complex Mo(N-2,4,6-Me 3 C 6 H 2 )Cl 3 (depe).…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Characterization, and MO Calculations of Vanadium Imido Complexes Containing Bidentate Phosphine Coligands

et al. 1999

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Treatment of complex V(N-2,6-(i)Pr(2)C(6)H(3))Cl(3) with 1,2-dimethoxyethane (dme) gives in quasi-quantitative yield the adduct V(N-2,6-(i)Pr(2)C(6)H(3))Cl(3)(dme) (1). Interaction of 1 with bidentate phosphines gives V(N-2,6-(i)Pr(2)C(6)H(3))Cl(3)(P-P) (P-P = depe, 2a; dppe, 2b) compounds. An X-ray analysis (monoclinic, space group P2(1)/c, a = 14.7387(14) Å, b = 10.6738(10) Å, c = 16.999(3) Å, beta = 90.954(2) degrees, Z = 4, R = 0.0544), carried out on complex 2a, shows a mer arrangement of the chloride ligands and a nonsymmetrical coordination of the diphosphine ligand. One of the phosphorus atoms occupies the trans position with respect to the organoimido ligand. MO calculations on the models V(NR)Cl(3)(H(2)PCH(2)CH(2)PH(2)) (R = H, C(6)H(5)) of complex 2a were performed. The mer isomer, which is more stable than the fac isomer, shows good agreement with the experimental data.

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Linear, Trinuclear Cobalt Complexes with o‐Phenylene‐bis‐Silylamido Ligands

Monakhov

Leusen

Kögerler

et al. 2017

Chemistry A European J

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Transamination of [Co{N(SiMe ) } ] with C H (NHSiiPr ) gave the centrosymmetric trinuclear [{Co N(SiMe ) (μ-η-[o-C H (κNSiiPr ) ])} Co ] (1) (Co , Co =terminal, internal Co, respectively), with 3-coordinate Co , and Co "sandwiched" between the o-phenylenes of the two ligands; experimental and computational data support Co centres and ditopic o-amido-imino-cyclohexen-allyl ligands; magnetic studies reveal intermetallic ferromagnetic interactions and single-molecule magnet (SMM) character. One-electron reduction of 1 yielded the salt [K(18-crown-6)(THF) ][{Co N(SiMe ) (μ-η-[o-C H (κNSiiPr ) ])} Co ] (4) with the anion isostructural to 1. The centrosymmetric Fe complex [{Fe N(SiMe ) (μ-η-[o-C H (κNSiiPr ) ])} Fe ] (5), analogous to 1, was also obtained.

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Synthesis, characterization, and X-ray crystal structures of W(VI) alkyl complexes with chelating diamide and imido co-ligands

Cited by 41 publications

References 21 publications

Metallacyclopentane Formation: A Deactivation Pathway for a Tungsten(VI) Alkylidene Complex in Olefin Metathesis Reactions

Metallacyclopentane Formation: A Deactivation Pathway for a Tungsten(VI) Alkylidene Complex in Olefin Metathesis Reactions

Synthesis, Structural Characterization, and MO Calculations of Vanadium Imido Complexes Containing Bidentate Phosphine Coligands

Linear, Trinuclear Cobalt Complexes with o‐Phenylene‐bis‐Silylamido Ligands

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