Control of slippage and conformation in indenyl complexes

Faller, J. W.; Crabtree, R. H.; Habib, Afroze

doi:10.1021/om00124a022

Cited by 183 publications

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“…The bonding of the hydrocarbon fragment to the molybdenum is an intriguing feature of this complex because of the possibility of distortions toward an η However, the average Μ-C(bridgehead) bond length is by only 0.058 Ä longer than the average Μ-C bond distances of the remaining three carbon atoms of the five-membered ring and the indenyl ligand is strictly planar, so the target compound features an essentially undistorted η 5 -indenyl molybdenum fragment [6]. The slight tilting of the indenyl ligand, resulting in the elongation of the Mo-C8 bond is assigned to the trans influence of the CO-ligand trans to the Mo-C8 bond [7,8]. …”

Section: Discussionmentioning

confidence: 99%

Crystal structure of (ƞ5-indenyl) (ƞ5-cyclopentadienyl) pentacarbonyl molybdenum ruthenium, (C5H5)(CO)2MoRu(CO)3(C9H7)

Straub¹,

Nissinen²

2005

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialInd(CO)3Mo-Ru(CO)2Cp was synthesized according to a modified procedure [1]. 3.0 ml (4.8 mmol) of a 1.6 Μ solution of nBuLi in hexanes were added dropwise to 0.6 ml (5.2 mmol) indene in 30 ml THF at -78 °C. After stirring for 3 h at RT, 1.056 g (4.0 mmol) Mo(CO)6 were added and the mixture refluxed for 24 h until the formation of NaMo(CO)3lnd was complete (IR control). A solution of 1.2 g (4.0 mmol) CpRu(CO)2Br [2] in 25 ml THF was added dropwise at RT, and it was refluxed until the starting materials were consumed (30 h, IR control). The solvents were removed at high vacuum and the residue extracted with 3 χ 50 ml hexane. The extracts were combined, filtered and the target compound crystallized at -20 °C. Slow recrystallization (flask in sealed dewar) by cooling from RT to -20 °C yielded crystals suitable for X-ray single-crystal diffraction. DiscussionThe title compound consists of a Mo(CO)3lnd and a Ru(CO>2Cp fragment, linked by an unsupported M-M' bond. The observed Mo-Ru bond length of3.0048(3) Ä is in the expected molybdenum-ruthenium single bond range [3]. The five caibonyl ligands are all essentially terminal, reflected by M(l)-M(2)-CO angles not smaller than 68.42(8)° and M-C-O angles larger than 171.9(2)°. However, in order to minimize oxygen contacts, two of the Mo-CO ligands are slightly more bent than the other carbonyl groups, and the short non-bonded contacts between C1 and C3 as well as between C2 and C4 (3.05 Ä and 3.07 A, respectively) are typical for this type of complex [1,4]. At room temperature, the carbon NMR spectra reveals a single resonance for all caibonyl groups, which indicates a facile and rapid CO interchange in and between the two metal moieties in solution. The >7 S cyclopentadienyl ligand adopts a centric co-ordination to the ruthenium, is located in trans position to the indenyl ligand relative to the Mo-Ru vector, and exhibits structural properties known from related compounds [3,5]. The bonding of the hydrocarbon fragment to the molybdenum is an intriguing feature of this complex because of the possibility of distortions toward an η (3) Ä. However, the average Μ-C(bridgehead) bond length is by only 0.058 Ä longer than the average Μ-C bond distances of the remaining three carbon atoms of the five-membered ring and the indenyl ligand is strictly planar, so the target compound features an essentially undistorted η 5 -indenyl molybdenum fragment [6]. The slight tilting of the indenyl ligand, resulting in the elongation of the Mo-C8 bond is assigned to the trans influence of the CO-ligand trans to the Mo-C8 bond [7,8].

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Section: Discussionmentioning

confidence: 99%

Crystal structure of (ƞ5-indenyl) (ƞ5-cyclopentadienyl) pentacarbonyl molybdenum ruthenium, (C5H5)(CO)2MoRu(CO)3(C9H7)

Straub¹,

Nissinen²

2005

Zeitschrift Für Kristallographie - New Crystal Structures

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“…Both the r/5-indenyl and the /z-r/5:l-indene-l,l-diyl ligands show a slight 'ring slippage' (Failer, Crabtree & Habib, 1985). The distances between the Mol atom and the C12, C13 and C14 atoms are on average 0.16A shorter than those to atoms C ll and C15.…”

Section: Commentmentioning

confidence: 93%

Photochemical Reactions of Transition Metal Organyl Complexes with Olefins. 15. Tricarbonyl(η4-1,3-butadiene)-μ-hydrido-(μ-η1:5-indene-1,1-diyl)(η5-indenyl)-dimolybdenum(Mo—Mo)

Kreiter¹,

Meuser²,

Frank³

et al. 1996

Acta Crystallogr C

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The Mo centres of the dinuclear title complex, [1(774) -1,3 -butadiene] tricarbonyl -1 nC, 2n 2 C-#-hydrido-[ 2 ( 1, -2,3,3a,7a-r/)-indenyl] [#-1 ( 1,2,3,3a,7a-~7): 2nC I -indenylidene]dimolybdenum(Mo--Mo), [Mo2 (H)(C9 H6)(C9 H7)-(C4H6)(CO)3], are bridged by a #-771:5-indene-l,1 -diyl and a ohydrido ligand. The Mo--Mo distance of 3.2024 (7)A is normal for an Mo---Mo single bond. cyclopentadienyl)dimolybdenum (Kern, 1992;Kreiter & Kern, 1993) are formed. The butadiene and 2-buten-1-ylidene ligands are formed by insertion of ethene into an Mo---C bond of the tetrahedral Mo2C2 core of compound (III) and successive metal-mediated hydride shifts.775-Indenyl complexes often show a different reaction behaviour from the corresponding r/5-cyclopentadienyl compounds because of the ability of the indenyl ligand to change its hapticity. In order to study the differences caused by indenyl ligands, tetracarbonyl(#-r/2:2-ethyne)-bis(r/5-indenyl)dimolybdenum, (II), was reacted photochemically with simple mono-olefins (Meuser, 1993). Compound (II) when reacted with ethene forms three butadiene complexes, namely, the title compound, (77 n-1,3-butadiene)tricarbonyl-#-hydrido-(#-r/1:5-indene -1,1-diyl)(775-indenyl)dimolybdenum, (I), (#-z/2:2-1,3-butadiene)tetracarbonylbis(r/5-indenyl)dimolybdenum, (IV), and ( #-r/2:2-1,3-butadiene )dicarbonylbis( 775-indenyl )-dimolybdenum, (V). The variability of the products reflects the different possibilities of coordination for the butadiene ligand at complex fragments with metal-metal single or triple bonds. In contrast to (~74-butadiene)tricarbonylbis(r/5-cyclopentadienyl)dimolybdenum, where the electron deficiency of the binuclear 32-electron complex is compensated for by a ~-r/2:1 -CO ligand, the comparable indenyl complex (I) is stabilized by the oxidative addition of a C--H bond of one indenyl ligand to the Mol atom. CommentWhen tetracarbonylbis075-cyclopentadienyl)(#-~72:2-ethyne)dimolybdenum, (III), is UV irradiated in the presence of ethene, the stable products (r/a-butadiene) -tricarbonylbis(r/5_cyclopentadienyl)dimolybdenum, (qa_ butadiene)tetracarbonylbis(r/5-cyclopentadienyl)dimolybdenum and (#-r/~:3-2-buten-l-ylidene)tetracarbonylbis(~75-

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“…(4) 1.978 (4) 1.957 (4) 1.960 (5) 1.934 (5) 1.947 (6) 1.932 (6) 1.979 (2) [e] Ω is the envelope fold angle defined as the angle between planes defined by C1, C2 and C3 and that of C1, C3, C4 and C5. [24] [f] Δ(M-C) represents the differences in the metal-carbon bonds. It is defined as the difference between the averages of the metal-carbon distances Mo-C4 and Mo-C5 and those of Mo-C1, Mo-C2 and M-C3.…”

Section: Indenyl Molybdenum Compounds With Intramolecular Coordinationmentioning

confidence: 99%

“…It is defined as the difference between the averages of the metal-carbon distances Mo-C4 and Mo-C5 and those of Mo-C1, Mo-C2 and M-C3. [24] [g] α is defined as absolute value of dihedral angle Cg(C3)-Mo1-N1-C11; [h] β is defined as absolute value of dihedral angle C1-C10-C11-N1. Indenyl complex bearing two pyridine arms 9 reacts with HBF4•Et2O to give dicationic species 17, see Scheme 8.…”

Section: Indenyl Molybdenum Compounds With Intramolecular Coordinationmentioning

confidence: 99%

Indenyl Compounds with Constrained Hapticity: The Effect of Strong Intramolecular Coordination

Mrózek¹,

Vinklárek²,

Růžičková³

et al. 2016

Eur J Inorg Chem

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A series of cyclopentadienyl and indenyl molybdenum(II) compounds with intramolecularly coordinated pyridine arm, including scorpionate-like species bearing two irreversibly coordinated arms on indenyl core, was synthesized and characterized. All presented structural types were confirmed by X-ray diffraction analysis. Due to π-basicity of pyridine, the intramolecular interaction is considerably stronger than in case of analogous species bearing tertiary amines in the side chain. Although the starting compounds for syntheses are isostructural, the reaction outcomes differ considerably. The cyclopentadienyl precursor gives a pentacoordinated η 5 :κN-compound while the indenyl analogue produces a hexacoordinated species with unprecedented η 3 :κN-coordination mode of the indenyl ligand representing an unusual example of so-called indenyl effect. The unusually high stability of η 3 :κN-coordination compounds toward η 3 to η 5 haptotropic rearrangement was clarified by theoretical calculations. As the strong intramolecular interaction prevents rotation of indenyl, it cannot reach a conformation suitable for η 3 to η 5 rearrangement. As a result, the low hapticity is effectively locked.

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Control of slippage and conformation in indenyl complexes

Cited by 183 publications

References 0 publications

Crystal structure of (ƞ5-indenyl) (ƞ5-cyclopentadienyl) pentacarbonyl molybdenum ruthenium, (C5H5)(CO)2MoRu(CO)3(C9H7)

Crystal structure of (ƞ5-indenyl) (ƞ5-cyclopentadienyl) pentacarbonyl molybdenum ruthenium, (C5H5)(CO)2MoRu(CO)3(C9H7)

Photochemical Reactions of Transition Metal Organyl Complexes with Olefins. 15. Tricarbonyl(η4-1,3-butadiene)-μ-hydrido-(μ-η1:5-indene-1,1-diyl)(η5-indenyl)-dimolybdenum(Mo—Mo)

Indenyl Compounds with Constrained Hapticity: The Effect of Strong Intramolecular Coordination

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