New syntheses and molecular structures of the decamethylmetallocene dicarbonyls (.eta.5-C5Me5)2M(CO)2 (M = titanium, zirconium, hafnium)

Sikora, David J.; Rausch, Marvin D.; Rogers, Robin D.; Atwood, Jerry L.

doi:10.1021/ja00395a068

Cited by 87 publications

(17 citation statements)

References 6 publications

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“…[11] The mean NbÀCO bond lengths are 2.057(7) , the OC-Nb-CO angle is 86.6(3)8. Angles in the same range have been found in the related compounds [Cp* 2 M(CO) 2 ] (M Ti, Zr, Hf) [12] 4 ]. [13] Recrystallisation of the dark precipitate described above from acetonitrile gave dark crystals with differing morphology.…”

Section: Resultssupporting

confidence: 68%

Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity

et al. 2000

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The reaction of [Cp#2NbTe2H] (1#; Cp# = Cp* (C5Me5) or Cp(x) (C5Me4Et)) with two equivalents of [Co2(CO)8] gives a series of cobalt carbonyl telluride clusters that contain different types of niobocene carbonyl fragments. At 0 degrees C, [Cp#2NbTe2CO3(CO)7] (2#) and [Co4Te2(CO)10] (3) are formed which disappear at higher temperatures: in boiling toluene a mixture of [cat2][Co9Te6(CO)8] (5#) (cat= [Cp#2Nb(CO)2]+) and [cat2][Co11Te7(CO)10] (6#) is formed along with [cat][Co(CO)4] (4#). Complexes 6# transform into [cat][Co11Te7(CO)10] (7#) upon interaction with HPF6 or wet SiO2. The molecular structures of 2(Cp(x)), 4(Cp(x)), 5(Cp*), 6(Cp*) and 7(Cp*) have been determined by X-ray crystallography. The structure of the neutral 2(Cp(x)) consists of a [Co3(CO)6Te2] bipyramid which is connected to a [(C5Me4Et)2Nb(CO)] fragment through a mu4-Te bridge. The ionic structures of 4(Cp(x)), 5(Cp*), 6(Cp*) and 7(Cp*) each contain one (4, 7) or two (5, 6) [Cp#2Nb(CO)2]+ cations. Apart from 4, the anionic counterparts each contain an interstitial Co atom and are hexacapped cubic cluster anions [Co9Te6(CO)8]2- (5) or heptacapped pentagonal prismatic cluster anions [Co11Te7(CO)10]n- (n=2: [6]2- , n=1: [7]-), respectively. Electrochemical studies established a reversible electron transfer between the anionic clusters [Co11,Te7(CO)10]- and [Co11Te7(CO)10]2in 6# and 7# and provided evidence for the existence of species containing [Co11Te7(CO),0] and [Co11Te7(CO)0]3-. The electronic structures of the new clusters and their relative stabilities are examined by means of DFT calculations.

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Section: Resultssupporting

confidence: 68%

Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity

et al. 2000

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“…• Similar OC-M -CO angles of 85 to 90° were crystallographically determined for (CsHshTi(COh, (CsHshZr(COh, (CsHshHf(COh and (CsHshV(CO)i [12][13][14], all of which accommodate one d 2 pair in their respective M(COh plane.…”

Section: Reaction Of (C5h5)2cr(co) With An Excess Of Comentioning

confidence: 70%

ansa-Metallocene derivatives

Raaij¹,

Brintzinger²

1988

Journal of Organometallic Chemistry

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“…138.8°) and 8 (138.8°) were found in a typical range of bent‐titanocene derivatives37 {Ti IV : [(η 5 ‐C 5 Me 5 )(η 5 ‐C 5 H 5 )TiCl 2 ] 132.0°,38 Ti III : [(η 5 ‐C 5 Me 4 H) 2 ‐TiCl] 139.1°,39 [(η 5 ‐C 5 Me 5 ) 2 TiCl] 143.6°40}. In contrast, the Ct*–Ti–Ct* angles in permethylated titanium( II ) complexes are usually significantly larger {[{(η 5 ‐C 5 Me 5 ) 2 ‐Ti} 2 (μ 2 ,η 1 ,η 1 ‐N 2 )] 145.7(3)°,33 [(η 5 ‐C 5 Me 5 ) 2 Ti(CO) 2 ] 147.9°41}. Also, in the case of the bulky fulvene complex 10 a larger value of 150.9° was found.…”

Section: Resultsmentioning

confidence: 99%

Low‐Valent Titanium–Pentafulvene Complexes — Formation of Dinuclear Titanium–Nitrogen Complexes

et al. 2005

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Sodium amalgam reduction of [(η5‐C5Me5)TiCl3] (1) in the presence of the pentafulvenes {C5H4=CR2, R: p‐tol (2), p‐FPh (3), CR2: adamantyl (4)} under nitrogen smoothly produces dark green or dark blue dinuclear low‐valent titanium complexes [{(η5‐C5Me5)Ti(η6‐C5H4=CR2)}2(μ2,η1,η1‐N2)] {R: p‐tol (6), p‐FPh (7), CR2: adamantyl (8)}, characterized by a bridging end‐on coordinated dinitrogen ligand, in high yield. In the same way, the nitrogen‐free, low‐coordinated complex [(η5‐C5Me5)Ti(η6‐C9H6=C(p‐tol)2)] (10) is obtained by using the more sterically demanding benzofulvene C9H6=C(p‐tol)2 (5) instead of 2–4. The solid‐state structures of the dinitrogen compounds reveal weakly activated end‐on bound N2 ligands with identical N–N distances of 1.160(3) Å (6) and 1.160(5) Å (8). The dinitrogen complexes 6, 7 and 8 show diamagnetic behaviour, which allowed a complete NMR spectroscopic characterization. So a correlation between the situation in solution, measured by NMR, and in the solid state (X‐ray diffraction) becomes possible and shows a congruent picture. A broad range of reactions can be imagined concerning the easily replaceable dinitrogen ligand as well as the known reactivity of fulvene ligands in complexes of early transition metals. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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New syntheses and molecular structures of the decamethylmetallocene dicarbonyls (.eta.5-C5Me5)2M(CO)2 (M = titanium, zirconium, hafnium)

Cited by 87 publications

References 6 publications

Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity

Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity

ansa-Metallocene derivatives

Low‐Valent Titanium–Pentafulvene Complexes — Formation of Dinuclear Titanium–Nitrogen Complexes

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