X-Ray molecular structure of tricarbonyl-(1–5,α-η-diphenylfulvene)chromium, [(η-C5H4CPh2)Cr(CO)3]

Andrianov, V. G.; Struchkov, Yuri T.; Setkina, V. N.; Zdanovich, V. I.; Zhakaeva, A.Zh.; Kursanov, Dmitri N.

doi:10.1039/c39750000117

Cited by 31 publications

(13 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[(η 6 -C 5 H 4 C(C 6 H 5 ) 2 )]Cr(CO 3 ) ( 28b ) was the first η 6 -fulvene complex studied by X-ray analysis (Figure 11A). This data experimentally confirmed the predicted tendency toward strong bending of C6 (Andrianov et al, 1975). The neutral complex 28b shows a bending angle of 28.4° with a Cr-C6 bond length of 2.55 Å, which can be explained by the HOMO obtained from extended Hückel calculations is shown in Figure 11D (Albright et al, 1978).…”

Section: π-Complexessupporting

confidence: 88%

Molecular Orbital Insights of Transition Metal-Stabilized Carbocations

2019

View full text Add to dashboard Cite

Transition metal-stabilized carbocations are characterized by synthetically valuable interactions, yet, to date there are no comprehensive reports of the many bonding modes that can exist between a metal and carbocation. This review summarizes developments in these complexes to provide a clear picture of their properties and reactivities. In order to strategically exploit them, we propose this summary of the different bonding modes for transition metal-carbocation complexes. These models will help chemists understand the orbital interactions involved in these compounds so that they can approach their synthetic goals most effectively. Multiple transition metals and carbocations will be discussed.

show abstract

Section: π-Complexessupporting

confidence: 88%

Molecular Orbital Insights of Transition Metal-Stabilized Carbocations

2019

View full text Add to dashboard Cite

show abstract

“…Fulvenes are popular ligands in organometallic chemistry, forming a variety of metal complexes having different coordination geometries. − Well-known complexes include [(η-C 5 H 4 CPh 2 )Cr(CO) 3 ], [(fulvene)M(CO) 3 ] (M = Cr, Mo), [(dimethylfulvene) 2 Fe 2 (CO) 5 ], and [Pt(η 2 -C 5 H 4 Ph 2 )(PPh 3 ) 2 ] . In this work we used 5-(propan-2-ylidene)cyclopenta-1,3-diene (6,6-dimethylfulvene) as a ligand to synthesize ruthenium complexes to be employed as thin-film precursors.…”

Section: Results and Discussionmentioning

confidence: 99%

Ruthenocene Precursors for Ruthenium-Containing Thin-Film Deposition: An Example of Solvent Nucleophilic Attack on Fulvene

et al. 2017

View full text Add to dashboard Cite

A new series of ruthenocene complexes were prepared from RuCl3·xH2O and 6,6-dimethylfulvene as potential precursors for thin-film deposition. The formation of these complexes was the result of an unforeseen nucleophilic attack of the solvent molecules (alcohols/amines) on the 6,6-dimethylfulvene ligand during the reaction. Complexes [RuII(C5H4C(CH3)2OCH3)2] (1), [RuII(C5H4C(CH3)2OC2H5)2] (2), [RuII(C5H4C(CH3)2N(CH3)2)2] (3), and [RuII(C5H4C(CH3)2N(CH2CH3)2)2] (4) were isolated in pure form and characterized by Fourier transform (FT) infrared and FT nuclear magnetic resonance spectroscopy as well as elemental and thermogravimetric (TG) analyses. Crystallographic studies of complexes 1–3 revealed a monomeric ruthenocene structure for all complexes and showed that the deprotonated alkylalkoxide or dialkylamide of the solvent molecule was attached to the exocyclic carbon of the fulvene ligand. Although the complexes were formed as ruthenocenes instead of the expected ruthenium fulvene complexes, they all displayed excellent stabilities and thermal properties. In particular, complexes 3 and 4 emerged as the best compounds owing to their clean TGA plot and excellent volatility, holding the potential as precursors for thin-film deposition.

show abstract

“…This also provides a convenient reference for a later comparison with the conformation of diferrocenyl ketone (see Discussion). Ring 1 is bent out of plane 5 by 24 of BF4-ions in the compounds they studied. The large Debye-Waller factors reported by Sime and Sime6a suggest disorder in their compound as well but this appears not to have been explored by them.…”

Section: Resultsmentioning

confidence: 99%

Structural studies of organometallic compounds. 3. Determination of the crystal structure of .alpha.,.alpha.-diferrocenylmethylium tetrafluoroborate, a stable carbenium ion salt, and a comparison of its structure with those of other organometallic carbenium cations

Cais¹,

Dani²,

Herbstein³

et al. 1978

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The crystal structure of the monoclinic polymorph of a,a-diferrocenylmethylium tetrafluoroborate ( a = 15.99, b = 12.75, c = 9.365 A, 6 = 90.6', space group P21/a, 4 formula units per cell) has been determined by standard methods using 2648 (222 with Iobsd = 0) intensities measured on a Weissenberg diffractometer using graphite-monochromated Mo Ka radiation. The final R factor was 9.3%. The cation has a transoid conformation, similar to that found for diferrocenyl ketone: the BF4-ions are orientationally disordered over three groups of sites. The ferrocenyl rings are bent at the a-carbon atoms so as to reduce the distances between the two Fe atoms and the exocyclic carbon atom to 2.69 and 2.81 A. Analogous distortions have been reported in the bis[(cyclopentadienyl)dicarbonyliron]propylenium cation (Fe --C+ distances 2.57,2.72 A) and to a lesser extent in other organometallic cations. We conclude that both metal-exocyclic carbon atom interaction, with resulting geometrical distortion of the cation, and delocalization of the positive charge over suitable regions of the cation lead to stabilization of organometallic carbenium cations.The exceptional stability of ferrocenylcarbenium ions has been considered a major factor governing the course of reaction in much of the organic chemistry of the ferrocenyl system leading to an intensive search for the sources of such ~tability.~ Success has not yet been achieved. In the hope that particular features of the geometry of such carbenium ions hold the clue to their stabilization, we have determined the crystal structure of the stable carbenium ion salt a,a-diferrocenylmethylium tetrafluoroborate (I). The results have been briefly r e p~r t e d .~ r (C0)S 1Tv V The other organometallic carbenium ion salts whose crystal structures have been reported are bis(a-cyclobutadienetricarbony1iron)phenylcarbenium tetrafluoroborate (11),5 ferrocenyldiphenylcyclopropenium tetrafluoroborate (III)? and bis[(cyclopentadienyl)dicarbonyliron]propylenium hexafluorophosphate7(IV). Intercomparison of all these results suggests that there are two interrelated factors which stabilize organometallic moiety in the delocalization of the positive charge, the other is the ability of the molecule to undergo geometrical changes which result in greater bonding interac-0002-7863/78/1500-5554$01 .OO/O tion between the metal atom and the formally positive ligand moiety. Experimental SectionThe (air-stable) title compound (see Figure 2 for crystallographic numbering) was synthesized by adaption of techniques developed by Cais and Eisenstadt8 and recrystallized from methanol. A number of salts were studied and the tetrafluoroborate was found to be the most stable and to give the best crystals for d i f f r a~t i o n .~ Two polymorphs were found, one monoclinic reported here in detail (Table I) andoneorthorhombic(a = 18.27(1),b = 1 1 . 8 8 ( 1 ) ,~= 8 . 9 8 ( 2 ) A , V = 1944 A3, dc&d = 1.59 g cm-3 for z = 4, d, , , , = 1.55 g cm-3).Unfortunately the orthorhombic crystal used for photography was lost before t...

show abstract

X-Ray molecular structure of tricarbonyl-(1–5,α-η-diphenylfulvene)chromium, [(η-C₅H₄CPh₂)Cr(CO)₃]

Abstract: In the title complex, the Cr(C0,) fragment is bonded to the six carbon atoms of the fulvene system, causing a significant distortion in planarity of the fulvene system, and a loss of C,, symmetry of the Cr(CO), fragment.

Cited by 31 publications

References 0 publications

Molecular Orbital Insights of Transition Metal-Stabilized Carbocations

Molecular Orbital Insights of Transition Metal-Stabilized Carbocations

Ruthenocene Precursors for Ruthenium-Containing Thin-Film Deposition: An Example of Solvent Nucleophilic Attack on Fulvene

Structural studies of organometallic compounds. 3. Determination of the crystal structure of .alpha.,.alpha.-diferrocenylmethylium tetrafluoroborate, a stable carbenium ion salt, and a comparison of its structure with those of other organometallic carbenium cations

Contact Info

Product

Resources

About