2021
DOI: 10.1002/chem.202103085
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Low‐Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments

Abstract: Low‐valent titanium species were prepared by reaction of [TiCp*X3] (Cp*=η5‐C5Me5; X=Cl, Br, Me) with LiEH4 (E=Al, B) or BH3(thf), and their structures elucidated by experimental and theoretical methods. The treatment of trihalides [TiCp*X3] with LiAlH4 in ethereal solvents (L) leads to the hydride‐bridged heterometallic complexes [{TiCp*(μ‐H)}2{(μ‐H)2AlX(L)}2] (L=thf, X=Cl, Br; L=OEt2, X=Cl). Density functional theory (DFT) calculations for those compounds reveal an open‐shell singlet ground state with a Ti−Ti… Show more

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Cited by 12 publications
(21 citation statements)
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“…The treatment of [Ti­(η 5 -C 5 H 5– n Me n )­Cl 3 ] ( n = 5, 4, 0) with finely powdered LiBH 4 (≥3 equiv) in toluene at room temperature afforded the titanium­(III) derivatives [{Ti­(η 5 -C 5 H 5– n Me n )­(BH 4 )­(μ-BH 4 )} 2 ] ( n = 5 ( 1 ), 4 ( 2 ), 0 ( 3 )) (Scheme ). We have previously reported the synthesis of 1 in 80% yield as a dark-blue pyrophoric solid, which melts at 67–68 °C . Complex 1 was also obtained in the attempted sublimation of [Ti­(η 5 -C 5 Me 5 )­(BH 4 ) 2 (thf)] (75 °C, 0.1 Torr) and was stable in benzene- d 6 solutions up to 65 °C .…”
Section: Resultsmentioning
confidence: 95%
See 1 more Smart Citation
“…The treatment of [Ti­(η 5 -C 5 H 5– n Me n )­Cl 3 ] ( n = 5, 4, 0) with finely powdered LiBH 4 (≥3 equiv) in toluene at room temperature afforded the titanium­(III) derivatives [{Ti­(η 5 -C 5 H 5– n Me n )­(BH 4 )­(μ-BH 4 )} 2 ] ( n = 5 ( 1 ), 4 ( 2 ), 0 ( 3 )) (Scheme ). We have previously reported the synthesis of 1 in 80% yield as a dark-blue pyrophoric solid, which melts at 67–68 °C . Complex 1 was also obtained in the attempted sublimation of [Ti­(η 5 -C 5 Me 5 )­(BH 4 ) 2 (thf)] (75 °C, 0.1 Torr) and was stable in benzene- d 6 solutions up to 65 °C .…”
Section: Resultsmentioning
confidence: 95%
“…Reduction of the latter titanium­(IV) trichloride precursor with an excess of magnesium led to a mixed-valence Ti II /Ti III trinuclear complex [{Ti­(η 5 -C 5 Me 5 )­(μ-Cl)} 3 (μ 3 -Cl)] capable of activating dinitrogen under ambient conditions . Analogous treatment of [Ti­(η 5 -C 5 Me 5 )­X 3 ] with excess LiAlH 4 in ethereal solvents (L) produced titanium­(II) species [{Ti­(η 5 -C 5 Me 5 )­(μ-H)} 2 {(μ-H) 2 AlXL} 2 ] (L = thf, X = Cl, Br; L = OEt 2 , X = Cl), while the reactions with the milder reductant LiBH 4 gave titanium­(III) tetrahydridoborato complexes . In particular, the X-ray crystal structure of the bis­(tetrahydridoborato) derivative showed a dimer [{Ti­(η 5 -C 5 Me 5 )­(BH 4 )­(μ-BH 4 )} 2 ] with two bridging BH 4 ligands between the metal centers (Scheme ).…”
Section: Introductionmentioning
confidence: 99%
“…There are three slightly different B−B distances in 1 , ranging from 1.784(9) to 1.817(8) Å, which are longer than those in [{Cp*Re} 2 {μ‐η 6 : η 6 ‐1,2‐B 6 H 4 Cl 2 }] [15] ( V ) (ranging from 1.700(18) to 1.780(16) Å). The Ti−B (ranging from 2.254(5) to 2.375(5) Å) and Ti−Ti (2.9307(12) Å) bond lengths in 1 are slightly shorter than those in [(Cp*Ti) 2 (B 2 H 6 ) 2 ] [20] (Ti−B: 2.386(4) and 2.400(3) Å; Ti−Ti: 2.936(1) Å).…”
Section: Figurementioning
confidence: 92%
“…1.700 (18) to 1.780(16) Å). The TiÀ B (ranging from 2.254(5) to 2.375(5) Å) and TiÀ Ti (2.9307(12) Å) bond lengths in 1 are slightly shorter than those in [(Cp*Ti) 2 (B 2 H 6 ) 2 ] [20] (TiÀ B: 2.386(4) and 2.400(3) Å; TiÀ Ti: 2.936(1) Å).…”
mentioning
confidence: 92%
“…Note that TiÀ B bonds are not shown for clarity. [20] (TiÀ B: 2.386(4) and 2.400(3) Å; TiÀ Ti: 2.936(1) Å).…”
mentioning
confidence: 99%