Synthesis and structure of [(η5-C5Me5)WCl2(μ-H)]2. A dinuclear tungsten hydride with a double bond formed from the reaction of BH3THF with (η5-C5Me5)WCl4

Peldo, Melanie A.; Shang, Maoyu; Fehlner, Thomas P.

doi:10.1016/s0022-328x(00)00084-x

Cited by 8 publications

(3 citation statements)

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“…The Lu−H av bond distances [2.28(4) Å] in 1b are slightly longer than those found in [Cp′Lu(μ-H) 2 ] 4 (THF) [Lu−(μ 2 -H) av = 2.16 Å], and [Cp′Lu(CH 2 SiMe 3 )(μ-H)(THF)] 2 [Lu−(μ 2 -H) av = 2.09(5) Å] . The W−H(1−2) av distances [1.82(4) Å] are similar to those in W 2 (μ-H) 2 Cl 4 (μ-dppm) 2 [1.79(8) Å; dppm = bis(diphenylphosphino)methane] and [Cp*WCl 2 (μ-H)] 2 [1.84(7) Å], whereas the W−H(3−6) av distances [1.71(4) Å] are slightly shorter. These observations suggest that bridging hydride ligands, Lu− H −W interact much more strongly with tungsten, which is consistent with the NMR results (see above).…”

Section: Resultsmentioning

confidence: 94%

Rare Earth/d-Transition Metal Heteromultimetallic Polyhydride Complexes Based on Half-Sandwich Rare Earth Moieties

Shima

Hou

2009

Organometallics

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The reaction of half-sandwich rare earth metal bis(alkyl) complexes Cp′Ln(CH 2 SiMe 3 ) 2 (THF) (Cp′ ) η 5 -C 5 Me 4 SiMe 3 ; Ln ) Y, Lu) with 1 equiv of the binuclear tungsten octahydride complex [Cp*WH 4 ] 2 (Cp* ) η 5 -C 5 Me 5 ) readily gave the corresponding Ln/W 2 heterotrimetallic hexahydride complexes Cp′Ln(THF)(µ-H) 6 (WCp*) 2 (Ln ) Y (1a), Lu (1b)) with release of SiMe 4 . A similar reaction of (C 5 Me 4 R)Ln(CH 2 SiMe 3 ) 2 (THF) with the binuclear osmium tetrahydride complex [Cp*OsH 2 ] 2 gave the Ln/Os 2 heterotrimetallic trihydride complexes [(Cp*Os){(µ-η 5 :η, in which one methyl carbon atom of the Cp* ligand on an Os center is bonded to the Ln atom through activation of the CsH bond. In contrast, the analogous reaction of (C 5 Me 4 R)Ln(CH 2 SiMe 3 ) 2 (THF) with the binuclear ruthenium tetrahydride complex [Cp*RuH 2 ] 2 gave the corresponding Ln/Ru 4 heteropentametallic heptahydride complexes (Cp*Ru) 4 -(C 5 Me 3 RCH 2 )Ln(µ-H) 7 (3a, Ln ) Y, R ) SiMe 3 ; 3b, Ln )Lu, R ) Me) as a result of removal of two protons from two molecules of [Cp*RuH 2 ] 2 by one molecule of (C 5 Me 4 R)Ln(CH 2 SiMe 3 ) 2 (THF) followed by oxidative addition of a methyl C-H bond of the (C 5 Me 4 R)Ln unit to a Ru center. The 1 H NMR spectra of 3a and 3b showed that oxidative C-H addition and C-H reductive elimination at the Ru atom are reversible in solution. Hydrogenolysis of 3a and 3b gave the decahydride complexes (Cp*Ru) 4 (Cp′Y)(µ-H) 10 (4a) and (Cp*Ru) 4 (Cp*Lu)(µ-H) 10 (4b), respectively. The molecular structures of 1b, 2b, 3a, 3b, 4a, and 4b were determined by X-ray analyses.

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Section: Resultsmentioning

confidence: 94%

Rare Earth/d-Transition Metal Heteromultimetallic Polyhydride Complexes Based on Half-Sandwich Rare Earth Moieties

Shima

Hou

2009

Organometallics

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“…[28] However, Fehlner et al later showed that the addition of monoboranes (LiBH 4 ·thf, BH 3 ·thf, or BHCl 2 ·SMe 2 ) to monocyclopentadienyl metal chlorides, [Cp*MCl] n , is an excellent method for the generation of metallaboranes containing transition metals from Group 5 to Group 9. [29] Although the methods described above were found to be suitable, and in a few instances, metal hydrides were discovered to be acceptable precursors for metallaboranes, [30][31][32][33][34][35] the reactions often led to various metallaboranes with low yields. Thus, the greatest challenge for chemists is to find new precursors for metallaboranes.…”

Section: Introductionmentioning

confidence: 99%

Metallaboranes from Metal Carbonyl Compounds and Their Utilization as Catalysts for Alkyne Cyclotrimerization

et al. 2014

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The photolysis of [M2(CO)10] (M=Re or Mn) with BH3⋅thf at room temperature yields arachno‐1 and 2, [(CO)8M2B2H6] (1: M=Re, 2: M=Mn). Both the compounds show a butterfly structure with seven skeletal electron pairs and 42 valence electrons. This result presents a new method for general access to low‐boron‐content metal–boron compounds without the cyclopentadienyl ligand at the metal centers. This new synthetic route is superior to the existing procedures because it avoids the use of [LiBH4] and metal polychlorides, for which the synthesis is very tedious. Compound 1 catalyzes the cyclotrimerization of a series of internal and terminal alkynes to yield mixtures of 1,3,5‐ and 1,2,4‐substituted benzenes. The reactivity of 1 with alkynes demonstrates for the first time that the introduction of the [B2H6] moiety into the [Re2(CO)10] framework significantly enhances the catalytic activity. Note that [Re2(CO)10] catalyzes the same set of alkynes under harsh conditions over a prolonged period of time. Quantum‐chemical calculations using DFT methods are applied to afford further insight into the electronic structure, stability, and bonding of 1 and 2. All the compounds are characterized by IR and 1H, 11B, and 13C NMR spectroscopy, and the geometry of 1 is established unambiguously through crystallographic analysis.

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“…[17, [22][23][24][25][26] One of our main objectives was to explore suitable metal precursors for metallaboranes containing metals from groups 5-9. Thus, in our continuing search for alternative metal precursors, containing the Cp*M fragment, we found that mono(halo)(cyclopentadienyl)metal carbonyl, [Cp*M(CO) n X] (M = Fe, X = I, n = 2; M = Mo or W, X = Cl, n = 3) are very useful to group 6 and 8 metallaboranes.…”

Section: Introductionmentioning

confidence: 99%

An Efficient Route to Group 6 and 8 Metallaborane Compounds: Synthesis of arachno‐[CpFe(CO)B₃H₈] and closo‐[(CpM)₂B₅H₉] (M = Mo, W)

et al. 2009

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Synthesis and structure of [(η5-C5Me5)WCl2(μ-H)]2. A dinuclear tungsten hydride with a double bond formed from the reaction of BH3THF with (η5-C5Me5)WCl4

Cited by 8 publications

References 20 publications

Rare Earth/d-Transition Metal Heteromultimetallic Polyhydride Complexes Based on Half-Sandwich Rare Earth Moieties

Rare Earth/d-Transition Metal Heteromultimetallic Polyhydride Complexes Based on Half-Sandwich Rare Earth Moieties

Metallaboranes from Metal Carbonyl Compounds and Their Utilization as Catalysts for Alkyne Cyclotrimerization

An Efficient Route to Group 6 and 8 Metallaborane Compounds: Synthesis of arachno‐[CpFe(CO)B₃H₈] and closo‐[(CpM)₂B₅H₉] (M = Mo, W)

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Synthesis and structure of [(η5-C5Me5)WCl2(μ-H)]2. A dinuclear tungsten hydride with a double bond formed from the reaction of BH3THF with (η5-C5Me5)WCl4

Cited by 8 publications

References 20 publications

Rare Earth/d-Transition Metal Heteromultimetallic Polyhydride Complexes Based on Half-Sandwich Rare Earth Moieties

Rare Earth/d-Transition Metal Heteromultimetallic Polyhydride Complexes Based on Half-Sandwich Rare Earth Moieties

Metallaboranes from Metal Carbonyl Compounds and Their Utilization as Catalysts for Alkyne Cyclotrimerization

An Efficient Route to Group 6 and 8 Metallaborane Compounds: Synthesis of arachno‐[Cp*Fe(CO)B3H8] and closo‐[(Cp*M)2B5H9] (M = Mo, W)

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An Efficient Route to Group 6 and 8 Metallaborane Compounds: Synthesis of arachno‐[CpFe(CO)B₃H₈] and closo‐[(CpM)₂B₅H₉] (M = Mo, W)