Reactive .pi.-complexes of the electron-rich transition metals.  3.  (.eta.4-Methylnaphthalene)iron(0) complexes.  X-ray crystal structure of (5-8-.eta.-1,4-dimethylnaphthalene)tris(trimethyl phosphite)iron

Schaeufele, Hartmut.; Hu, Dongqi; Pritzkow, Hans; Zenneck, Ulrich

doi:10.1021/om00104a019

Cited by 46 publications

(16 citation statements)

References 3 publications

(4 reference statements)

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“…[4] For example, proton-coupled 13 C NMR spectra of these species show only one singlet between 150-155 ppm, which is in the characteristic region for quaternary carbons in 1,2,3,4-h 4 -anthracene (bound ring only) and h 4 -naphthalene complexes. [16,17] Single-crystal X-ray structural characterizations of the zirconate 3 and hafnates 4 and 6 confirmed the deductions from solution NMR data about the nature of these anions. In particular, the anthracenemetalates 3 and 4 contain three essentially identical h 4 -anthracene groups coordinated through an outer ring to Zr and Hf in a trigonal prismatic array.…”

supporting

confidence: 59%

Structurally Distinct Homoleptic Anthracene Complexes, [M(C₁₄H₁₀)₃]²⁻, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

et al. 2008

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Being positive about anions: Hydrocarbon complexes containing negative‐valent Hf are obtained for the first time as tris(polyarene)hafnates(2−), polyarene=anthracene (An) and naphthalene, where the latter functions as a synthon for the unknown atomic Hf2− (see scheme, cot=1,3,5,7‐cyclooctatetraene). Tris(anthracene)metalates(2−) of Ti and Zr were also accessed, which completes an unprecedented triad of tris(arene)metal complexes.

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supporting

confidence: 59%

Structurally Distinct Homoleptic Anthracene Complexes, [M(C₁₄H₁₀)₃]²⁻, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

et al. 2008

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“…1 H and 13 C NMR spectra of 1 were independent of the cation and established that its stoichiometry in solution is identical to that observed in the solid state (vide infra). 1 H, 13 C correlated NMR spectra of 1 exhibited two equally intense quaternary 13 C signals at δ =134.1 and 146.0, which are indicative of two equivalent η 4 ‐anthracenes bound through one peripheral ring each to cobalt 8 . 1 H NMR spectra of 1 are also consistent with the presence of two identical anthracene groups bound in the same fashion to cobalt (see Experimental Section).…”

Section: Methodsmentioning

confidence: 99%

Bis(1,2,3,4-η4-anthracene)cobaltate(1−)

2002

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Polycyclic aromatic hydrocarbon (PAH or polyarene) [1] anion mediated reductions of transition metal halides and related substances provide convenient and sometimes unique routes to a variety of polyarene metal complexes and derived species. [2] Since the polyarene ligands may be labile and easily displaced by a variety of small molecules, polyarene metal complexes are potential sources of highly unsaturated metallic units in chemical synthesis. [3] Homoleptic systems are of particular interest since these species may function as ™naked∫ metal atom reagents and are therefore valuable precursors for the general exploration of low-valent transition metal chemistry. [4] Except for the first reported homoleptic polyarene transition metal complex [Ru(C 10 H 8 ) 2 ] 2 (C 10 H 8 naphthalene), [5] all previous examples contained only early (Groups 4 ± 6) transition metals. [4] However, the existence of this cationic ruthenium species suggested that related neutral and anionic polyarene complexes of later transition metals should also be accessible. We now report on the first anion of this type and the initial homoleptic polyarene complex of cobalt, bis(h 4 -anthracene)cobaltate(1 À ) (1). The only previously known homoleptic anthracene transition metal complex is bis(anthracene)chromium(0), which was prepared by the reaction of chromium vapor and anthracene in a metal atom reactor. [4c] Reduction of cobalt(ii) bromide by three equivalents of potassium anthracene in tetrahydrofuran (THF) at À 55 to À 65 8C provided a dark red solution, from which deep red, nearly black, microcrystals of 1 as [K([2.2.2]cryptand)] or [K([18]crown-6)(THF) 2 ] salts were isolated in 82 ± 87 % yields (see Experimental Section for details; [Eq. (1)]).Corresponding reductions conducted with alkali metal naphthalenes provided much less thermally stable solutions of a presumably analogous bis(naphthalene)cobaltate(1 À ).

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“…A comparable gradation of the chemical shifts is found for protons H1 and H2 of the diene fragment of the iron naphthalene complexes 7 and 8 as well as for a variety of other iron-coordinated dienes (see Table 1). [19][20][21] Metal coordination comparable to that in 3 in which opposite sides of the decacyclene ligand are complexed by two metal/ligand fragments was found for Ni 2 decacylene complex 5 [10] and Co 2 decacylene complex 6. [11] Interestingly, crystal batches obtained from reaction (2) gave low yields of crystals of the larger, tetranuclear aggregate 4 in addition to the dinuclear main product 3.…”

Section: Resultsmentioning

confidence: 69%

“…Here positions C1 and C4 are shifted to high field by about 20 ppm compared to C2, C3, C5, and C6, in full agreement with other h 4 -naphthalene iron complexes. [19,20] Their signals are found in the same characteristic shift region for complexed versus uncomplexed carbon positions. Consistent with the twofold complexation of two of the three naphthalene subunits of 4 is also the agreement with data reported for the closely related [(h 5 -Cp R Fe) 2 (m 2 -naphthalene)] (R = H 5 , Me 5 ) complexes 7 [16,17] and 8 [18] (Table 1).…”

mentioning

confidence: 77%

Decacyclene as Complexation Manifold: Synthesis, Structure and Properties of Its Fe₂ and Fe₄ Slipped Triple‐Decker Complexes

Schneider

Spickermann

Lehmann

et al. 2006

Chemistry A European J

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Reaction of [(eta(5)-Me4EtC5)Fe(II)Cl(tmeda)] (tmeda = N,N,N'N'-tetramethylethylenediamine) with a polyanion solution of decacyclene (1) results in the formation of the triple-deckers [{(eta(5)-Me4EtC5)Fe}2-mu2-(eta(6):eta(6)-decacyclene)] (3) and [{(eta(5)-Me4EtC5)Fe}4-mu4-(eta(6):eta(6):eta(6):eta(6)-decacyclene)] (4). Metal complexation in 3 and 4 occurs on opposite faces of the pi perimeter in an alternating mode. The decacyclene ring adopts a gently twisted molecular propeller geometry with twofold crystallographic symmetry (C2). Complex 4 crystallizes in the chiral space group C222(1); the investigated crystal only contains decacyclene rings with M chirality. The handedness can be assigned unambiguously to the presence of the iron atoms. Cyclovoltammetric studies revealed quasireversible behavior of the redox events and a strong interaction of the Fe atoms in 3 and 4, exemplified by potential differences deltaE of 660 and 770(780) mV between the first and the second individual oxidation processes. This corresponds to a high degree of metal-metal interaction for 3 and 4. The successful syntheses of 3 and 4 together with earlier results from our laboratory proves that all five- and six-membered pi subunit sets of 1 are prone to metal complexation. A clear site preference in 1 towards the complexation of [Cp(R)]iron, -cobalt, and -nickel fragments exists.

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Reactive .pi.-complexes of the electron-rich transition metals. 3. (.eta.4-Methylnaphthalene)iron(0) complexes. X-ray crystal structure of (5-8-.eta.-1,4-dimethylnaphthalene)tris(trimethyl phosphite)iron

Cited by 46 publications

References 3 publications

Structurally Distinct Homoleptic Anthracene Complexes, [M(C₁₄H₁₀)₃]²⁻, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

Structurally Distinct Homoleptic Anthracene Complexes, [M(C₁₄H₁₀)₃]²⁻, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

Bis(1,2,3,4-η4-anthracene)cobaltate(1−)

Decacyclene as Complexation Manifold: Synthesis, Structure and Properties of Its Fe₂ and Fe₄ Slipped Triple‐Decker Complexes

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Reactive .pi.-complexes of the electron-rich transition metals. 3. (.eta.4-Methylnaphthalene)iron(0) complexes. X-ray crystal structure of (5-8-.eta.-1,4-dimethylnaphthalene)tris(trimethyl phosphite)iron

Cited by 46 publications

References 3 publications

Structurally Distinct Homoleptic Anthracene Complexes, [M(C14H10)3]2−, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

Structurally Distinct Homoleptic Anthracene Complexes, [M(C14H10)3]2−, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

Bis(1,2,3,4-η4-anthracene)cobaltate(1−)

Decacyclene as Complexation Manifold: Synthesis, Structure and Properties of Its Fe2 and Fe4 Slipped Triple‐Decker Complexes

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Structurally Distinct Homoleptic Anthracene Complexes, [M(C₁₄H₁₀)₃]²⁻, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

Structurally Distinct Homoleptic Anthracene Complexes, [M(C₁₄H₁₀)₃]²⁻, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

Decacyclene as Complexation Manifold: Synthesis, Structure and Properties of Its Fe₂ and Fe₄ Slipped Triple‐Decker Complexes