Synthese und Molekülstruktur von [{Cp′(μ-η1 : η5-C5H3Me)Mo(μ-AlRH)}2] (Cp′ = C5H4Me, R =iBu, Et)

Abstract

[Cp′2MoH2] reagiert mit HAlR2 zu [{Cp′(μ‐η1 : η5‐C5H3Me)Mo(μ‐AlRH)}2] (Cp′ = C5H4Me, R = iBu (1), Et (2)). [Cp′2MoH2] und 1 wurden röntgenstrukturanalytisch charakterisiert. In 1 liegt eine direkte Mo–Al‐Bindung vor (2,636(2) Å).

Reactivity and Properties of [−O−BiIII...OMo−]nChains

“…In 4 , the common structure of M(IV) Cp 2 ML 2 complexes is retrieved with a bent-sandwich configuration of the cyclopentadienyl ligands about the metal. The bending angle in 4 is 145.3°; thus it compares well with the value of 145.8° in [Cp 2 MoH 2 ]30a or 143.3° in XV , but is slightly smaller than the one in [ Me Cp 2 MoH 2 ] (149.5(1)°) 30b. The Mo−Bi bond length amounts to 2.8976(3) Å and is thus similar to those found in the other compounds with bismuth atoms bonded to the Cp 2 Mo or Me Cp 2 Mo moieties.…”

“…These range from 2.788(2) Å in [Cp 2 Mo{Bi(OCH(CF 3 ) 2 ) 2 } 2 ] 28a to 2.966(2) Å in the tetranuclear compound [{Cp 2 Mo} 2 {μ-Bi(O t Bu)} 2 ],28b which has a structure similar to that of XVI . The Mo−H bond length of 1.56(5) Å is significantly shorter than that in [Cp 2 MoH 2 ] (neutron diffraction, 1.685(3) Å) 30a or [ Me Cp 2 MoH 2 ] (1.63(3) Å) 30b. The only known homologous molybdocenemonohydrides that have so far been structurally characterized appear to be [Cp 2 Mo(H)(μ-PPh 2 )Mn(CO) 2 Cp] and the ionic complex [Cp 2 Mo(H)(PPh 3 )]I, while no compounds containing one As or Sb atom bonded to the Mo center are known.…”

Al–H σ-bond coordination: expanded ring carbene adducts of AlH3 as neutral bi- and tri-functional donor ligands

“…24 The Mo-Al distances for 3a and 3b [2.621(1), 2.594(1) Å] can be compared to those reported for Mo-Al single bonds [e.g. 2.636(2) Å for {Cp 0 (m-Z 1 :Z 5 -C 5 H 3 Me)Mo(m-Al i BuH} 2 ], 30 being significantly shorter than the sum of the covalent radii (2.75 Å). 31 Moreover, these distances are consistent with the Cr-Al contact measured for the 24 when due allowance is made for the differing radii of the group 6 metals (Dr = 0.15 Å).…”

12 Chromium, molybdenum and tungsten

“…The crystal structure was also determined for the [(η 5 -C 5 H 4 Me) 2 MoH 2 ] starting material. 15 The alkoxo complexes [Cp 2 W(PMe 3 )(OR)](OTs) (R = Me, Et, Pr n , Pr i ) have been prepared. The β-elimination of these complexes in dmso yields the mono-hydrido complex, [Cp 2 W(H)(PMe 3 )](OTs).…”