The structures of bis[η5-(1-cyclopentadienyl-2-iodoethane)]diiodomolybdenum and bis[η5-(2-cyclopentadienylethyl)]molybdenum

Gourdon, André; Prout, Keith

doi:10.1107/s0567740881007814

Cited by 7 publications

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“…Mo-C distances [range 2.23 (2)-2.29 (2)A, mean 2.25 ,/k] compare well with those in the 17-electron cation [Mo(acac)(H20)(rf-cht)] + (Green, Kirsch, Stone & Welch, 1977) [mean 2.265 (15) ,/k] and are on average shorter than the corresponding values observed in the 18-electron compounds [Mo(a-C6Fs)(CO)E(r/7cht)], mean 2.316A (Churchill & O'Brien, 1969), [MoX(CO)2~(r/7-cht)] with X = C1 or Br, mean 2.321 and 2.337 A respectively (Ziegler, Sasse & Nuber, 1975). It is not possible to relate the slight variations in (Gourdon & Prout, 1981) but longer than in the 16-electron complex [{(r/5-CsHs)Mo(NO)I}2(CH3) 2-N 2] [2.735 (1) and 2.767 (1)A] (Mallinson, Sim & Woodhouse, 1980). The distances between the two I atoms within a molecule are surprisingly short [3.897 (1) and 3.862 (2) A] if compared with the sum of the van der Waals radii (4.…”

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confidence: 86%

Structure of (η⁷-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum

Gourdon¹,

Prout²

1982

Acta Crystallogr Sect B

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confidence: 86%

Structure of (η⁷-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum

Gourdon¹,

Prout²

1982

Acta Crystallogr Sect B

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“…So weichen Kippwinkel a = 20.48(7)8 und Deformationswinkel d = 159.418 von 3 deutlich von den entsprechenden Werten für 1 und 4 ab, obwohl die Mo-X Cp -Abstände der h 5 -koordinierten Cyclopentadienylliganden von 3 (1.942(6), 1.941(6) ) mit denen von 1 (1.952(8), 1.954(8) ) und 4 (1.942, 1.942 ) vergleichbar sind. [12] Die Mo-Si-Abstände sind mit 2.4915 (4) [13] Weiterhin ist eine Reihe von Fulvenkomplexen, vor allem von frühen Übergangsmetallen, bekannt, die Liganden vom Typ C 5 R 4 =CR' 2 aufweisen (R = H, Me; R' = H, verschiedene organische Gruppen). Experimentelle und theoretische Untersuchungen zeigten, dass der Koordinationsmodus des Fulvenliganden zwischen einer dianionischen h 1 ,h 5 -und einer olefinischen h 6 -Koordination liegt; somit besteht im erstgenannten Fall eine gewisse Verwandtschaft mit der Titelverbindung.…”

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Intramolekulare Aktivierung eines Disila[2]molybdänocenophandihydrids – Synthese und Struktur eines [1],[1]Metalloarenophans

et al. 2008

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Intramolecular Activation of a Disila[2]molybdenocenophanedihydride: Synthesis and Structure of a [1],[1]Metalloarenophane

et al. 2008

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Metallocenophanes have attracted increasing attention in recent years, as strained ansa complexes have become pivotal precursors for organometallic polymers prepared by ringopening polymerization (ROP), whereas unstrained metallocenophanes, especially those derived from Group 4 metals, serve as catalysts for olefin polymerization.[1]The structural and electronic properties and the particular reactivity of ansa complexes are in the focus of current research. The reactivity of the EÀC ipso bond (E = bridging element, C ipso = ipso carbon atom of the cyclopentadienyl ring) is of major importance for ROP, which can be induced thermally, by interaction with nucleophiles, or by latetransition-metal catalysts.[1a-e] Furthermore, ligand exchange reactions, which play a role in catalytic processes, [1f-h, 2] as well as haptotropic shifts of cyclopentadienyl ligands under different conditions [3] are being intensely studied. [2]Metallocenophanes, which are not commonly susceptible to ROP owing to their lower molecular strain, nevertheless attracted considerable attention because of their pronounced propensity to oxidatively add to coordinatively unsaturated complexes of late-transition-metal elements through the bridging EÀE (E = B, Si, Sn) moiety. Owing to the facile activation of the E À E bond by, for example, Pd 0 and Pt 0 , subsequent insertions of various unsaturated organic substrates have been achieved. In 1992, Manners and coworkers reported the first Pd-catalyzed insertion of alkynes into the SiÀSi bridge of tetramethyldisila[2]ferrocenophane, [4] Herberhold et al. described in 1997 the first oxidative addition of a Pt 0 fragment into the SnÀSn bridge of an ansaferrocene and the subsequent insertion of an alkyne, [5] whereas our group accomplished oxidative additions of Pt 0 fragments as well as homogeneously and heterogeneously catalyzed insertions of alkynes and diazobenzene into BÀB and SiÀSi bonds of various [2]metalloarenophanes. [6] Motivated by this facile activation of the EÀE bridge, we wondered whether a corresponding oxidative addition can be achieved intramolecularly and turned our attention to tetramethyldisila[2]molybdenocenophanedihydride (1) as a promising starting material. Herein we report the synthesis and full characterization of this species and its conversion into an unprecedented twofold-bridged [1],[1]metalloarenophane.Compound 1 was synthesized by dilithiation of 1,2-bis(cyclopentadienyl)tetramethyldisilane in toluene/diethyl ether (9:1) at 0 8C and subsequent reaction with MoCl 5 at À78 8C in the presence of NaBH 4 as a reducing agent in THF/ hexane (4:1) (Scheme 1).The very air-sensitive but moisture-stable compound 1 was obtained as a yellow solid in 29 % yield and was characterized by multinuclear NMR spectroscopy in solution. Two characteristic virtual triplets for the C 5 H 4 ligands at d = 4.72 and 4.70 ppm, one singlet for the methyl groups at d = 0.17 ppm, and one signal for the hydrogen atoms at d = À8.20 ppm are observed in the 1 H NMR spectrum, thus indicating C 2v symmetr...

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The structures of bis[η5-(1-cyclopentadienyl-2-iodoethane)]diiodomolybdenum and bis[η5-(2-cyclopentadienylethyl)]molybdenum

Abstract: ExperimentalThe crystal structures of the title compounds have been

Cited by 7 publications

References 5 publications

Structure of (η⁷-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum

Structure of (η⁷-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum

Intramolekulare Aktivierung eines Disila[2]molybdänocenophandihydrids – Synthese und Struktur eines [1],[1]Metalloarenophans

Intramolecular Activation of a Disila[2]molybdenocenophanedihydride: Synthesis and Structure of a [1],[1]Metalloarenophane

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The structures of bis[η5-(1-cyclopentadienyl-2-iodoethane)]diiodomolybdenum and bis[η5-(2-cyclopentadienylethyl)]molybdenum

Abstract: ExperimentalThe crystal structures of the title compounds have been

Cited by 7 publications

References 5 publications

Structure of (η7-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum

Structure of (η7-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum

Intramolekulare Aktivierung eines Disila[2]molybdänocenophandihydrids – Synthese und Struktur eines [1],[1]Metalloarenophans

Intramolecular Activation of a Disila[2]molybdenocenophanedihydride: Synthesis and Structure of a [1],[1]Metalloarenophane

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Structure of (η⁷-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum

Structure of (η⁷-cycloheptatrienyl)diiodo(tetrahydrofuran)molybdenum