Structure of bis(μ-ethylideneamido)-bis(tricarbonyliron)(Fe–Fe)

Gervasio, Giuliana; Stanghellini, P. L.; Rossetti, R.

doi:10.1107/s0567740881005505

Cited by 16 publications

(7 citation statements)

References 6 publications

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“…Only four compounds containing Fe−Fe bonds doubly-bridged by nitrogen, where the nitrogen atoms are double bonded to a carbon atom, have been structurally characterized. The Fe−Fe bonds are again shorter than those in 5 , 2.439 Å in Fe 2 (CO) 6 (μ-NC 6 H 10 ) 2 ,13a 2.403 Å in Fe 2 (CO) 6 (μ-NCPh 2 ) 2 ,13b 2.393 Å in Fe 2 (CO) 6 (μ-N 2 C 23 H 18 ),13c and 2.415 Å in Fe 2 (CO) 6 (μ-NCHMe) 2 13d…”

Section: Discussionmentioning

confidence: 89%

“…The reaction of 2-methylbenzotellurazole with Fe 3 (CO) 12 afforded three isolable pure fractions. One was the purple Fe 3 Te 2 (CO) 9 , the second ( 6 ) was another purple material of complex structure (Figure ), and the third was the red azaferrole (Figure ). It is probable that the three compounds can be considered to arise at various stages of a complex parallel reaction sequence involving the detelluration of the heterocycle and the replacement of the tellurium by, interestingly, both an iron atom and an inserted carbonyl group.…”

Section: Discussionmentioning

confidence: 99%

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Reaction of Fe₃(CO)₁₂ with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

et al. 1997

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Heterocyclic tellurium compounds containing both tellurium and nitrogen in the heterocyclic ring are shown to be useful precursors for the synthesis of novel organoiron compounds. Thus, reaction of Fe3(CO)12 with benzoisotellurazole yields (C6H4CHNTe)2Fe3(CO)7, 5. The structure of 5 was established by X-ray crystallography; it is based on a nonlinear chain of three iron atoms, Fe1−Fe2−Fe3 133.4(1)°, with Fe1−Fe2, 2.472(2) Å doubly-bridged by nitrogen and Fe2−Fe3, 2.683(2) Å, doubly-bridged by tellurium. The reaction of Fe3(CO)12 with 2-methylbenzotellurazole results in two new crystalline products C18H7NFe3O10, 6, and C14H7NFe2O6, 7, involving detelluration of the heterocycle. X-ray crystallography shows that 6 contains a triangular arrangement of iron atoms, two edges of which are bridged respectively by the nitrogen and carbon atoms of the NC formal double bond and the latter edge is also bridged by a carbonyl in an almost symmetrical manner. The third edge of the iron triangle is not directly bridged, and at 2.647(1) Å, it is the longest edge of the triangle. In 7, one iron atom forms part of a benzoferrazole system, and the second iron is π-bonded to the CCNC residue of the ferrazole with a relatively short Fe−Fe contact of 2.498(1) Å.

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Section: Discussionmentioning

confidence: 89%

Section: Discussionmentioning

confidence: 99%

Reaction of Fe₃(CO)₁₂ with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

et al. 1997

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“…8a,f Most recently, we found a new method for the preparation of dimetal bridging carbene complexes: the reactions of diiron cationic carbyne complexes, [Fe 2 (µ-CO)(µ-CAr)(CO) 2 (η 5 -C 5 H 5 ) 2 ]BBr 4 (1, Ar ) Ph; 2, Ar ) p-MeC 6 H 4 ), with anionic carbonylmetal nucleophiles. For instance, the cationic carbyne complexes 1 and 2 Organometallics 2000, 19 ) 2 ] (eq 2). 9 This offers a new and useful method for the preparation and structural modification of dimetal bridging carbene complexes.…”

Section: Introductionmentioning

confidence: 99%

Unusual Reactions of Cationic Bridging Carbyne Complexes of Bis(η⁵-cyclopentadienyl)diiron Tricarbonyl with Carbonylmetal Anions. A Route to Diiron Bridging Carbyne Complexes

2000

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The reactions of cationic carbyne complexes of diiron, [Fe 2 (µ-CO)(µ-CPh)(CO) 2 (η 5 -C 5 H 5 ) 2 ]-BBr 4 (1), with the anionic carbonylmetal compounds Na[M(CO) 5 CN] (3, M ) Cr; 4, M ) Mo; 5, M ) W) in THF at low temperature afford the novel bridging carbyne complexes [Fe 2 (µ-CO)(µ-CPh)(CO) 2 (η 5 -C 5 H 5 ) 2 NCM(CO) 5 ] (6, M ) Cr; 7, M ) Mo; 8, M ) W). In contrast to the reaction of 1, the cationic carbyne complex [Fe 2 (µ-CO)(µ-CC 6 H 4 Me-p)(CO) 2 (η 5 -C 5 H 5 ) 2 ]BBr 4 (2) reacts with carbonylmetal anions 3-5 under the same conditions to produce the novel bridging p-tolyl(pentacarbonylcyanotungsten)carbene complexes [Fe 2 (µ-CO){µ-C(C 6 H 4 Mep)(CO) 2 (η 5 -C 5 H 5 ) 2 NCM(CO) 5 }] (9, M ) Cr; 10, M ) Mo; 11, M ) W). However, the analogous reaction of Na[Fe(CO) 4 CN] with 1 yields the diiron bridging phenylcarbene complex [Fe 2 -(µ-CO){µ-C(H)Ph}(CO) 2 (η 5 -C 5 H 5 ) 2 ] (12). The structures of 7, 8, and 11 have been established by X-ray crystallography.a Estimated standard deviations in the least significant figure are given in parentheses.

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“…The N atom is now coordinated to Fe(2), to which it provides two electrons to satisfy the 18-electron rule. The Fe(2)ÀN(1) bond length is 1.966(11) ä, which is somewhat shorter than the Fe À N bond lengths in diiron complexes with a bridging RCNR(E) unit: [(m-p-MeC 6 H 4 -Te)(m-PhCNPh)Fe 2 (CO) 6 ] (1.993(4) ä), [23] [Fe 2 (CO) 4 (m 2 -RNCH)(m-PCy 2 )(m-dppm)] (R allyl) (2.015(13) ä), [24] and [(m-PhSe)(s,m-PhCNPh)Fe 2 (CO) 6 ](2.000(3) ä), [25] but it is nearly the same as that in the diiron-bridging carbyne complex [Fe 2 (m-CO)(m-CC 6 H 5 )(CO) 2 6 (N CHCH 3 ) 2 ] (1.942(7) ä), [26] in which closing of the Fe 2 N 2 core with shorter FeÀN bond lengths results in partial double-bond character in the FeÀN bonds. The shorter Fe(2)ÀN distance suggests that there is some double-bond character in the Fe(2)ÀN bond in 21.…”

Section: Resultsmentioning

confidence: 83%

Remarkable Reactions of Cyclooctatetraene Diiron‐Bridging Carbyne Complexes with Amino and Amido Compounds: Nucleophilic Addition to and Breaking of the Cyclooctatetraene Ring

Zhang

Sun

et al. 2003

Chemistry A European J

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The reactions of the cationic, diiron-bridging carbyne complexes [Fe(2)(mu-CAr)(CO)(4)(eta(8)-C(8)H(8))]BF(4) (1, Ar=C(6)H(5); 2, Ar=p-CH(3)C(6)H(4); 3, Ar=p-CF(3)C(6)H(4)) with LiN(C(6)H(5))(2) in THF at low temperature gave novel N-nucleophilic-addition products, namely, the neutral, diiron-bridging carbyne complexes [Fe(2)(mu-CAr)(CO)(4)(eta(7)-C(8)H(8)N(C(6)H(5))(2))] (4, Ar=C(6)H(5); 5, Ar=p-CH(3)C(6)H(4); 6, Ar=p-CF(3)C(6)H(4))). Cationic bridging carbyne complexes 1-3 react with (C(2)H(5))(2)NH, (iC(3)H(7))(2)NH, and (C(6)H(11))(2)NH under the same conditions with ring cleavage of the COT ligand to produce the novel diiron-bridging carbene inner salts [Fe(2)[mu-C(Ar)C(8)H(8)NR(2)](CO)(4)] (7, Ar=C(6)H(5), R=C(2)H(5); 8, Ar=p-CH(3)C(6)H(4), R=C(2)H(5); 9, Ar=p-CF(3)C(6)H(4), R=C(2)H(5); 10, Ar=C(6)H(5), R=iC(3)H(7); 11, Ar=p-CH(3)C(6)H(4), R=iC(3)H(7); 12, Ar=p-CF(3)C(6)H(4), R=iC(3)H(7); 13, Ar=C(6)H(5), R=C(6)H(11); 14, Ar=p-CH(3)C(6)H(4), R=C(6)H(11), 15, Ar=p-CF(3)C(6)H(4), R=C(6)H(11)). Piperidine reacts similarly with cationic carbyne complex 3 to afford the corresponding bridging carbene inner salt [Fe(2)[mu-C(Ar)C(8)H(8)N(CH(2))(5)](CO)(4)] (16). Compound 9 was transformed into a new diiron-bridging carbene inner salt 17, the trans isomer of 9, by heating in benzene. Unexpectedly, the reaction of C(6)H(5)NH(2) with 2 gave a novel COT iron-carbene complex [Fe(2)[=C(C(6)H(4)CH(3)-p)NHC(6)H(5)](mu-CO)(CO)(3)(eta(8)-C(8)H(8))] (18). However, the analogous reactions of 2-naphthylamine with 2 and of p-CF(3)C(6)H(4)NH(2) with 3 produce novel chelated iron-carbene complexes [Fe(2)[=C(C(6)H(4)CH(3)-p)NC(10)H(7)](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (19) and [Fe(2)[=C(C(6)H(4)CF(3)-p)NC(6)H(4)CF(3)-p](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (20), respectively. Compound 18 can also be transformed into the analogous chelated iron-carbene complex [Fe(2)[=C(C(6)H(4)CH(3)-p)NC(6)H(5)](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (21). The structures of complexes 6, 9, 15, 17, 18, and 21 have been established by X-ray diffraction studies.

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Structure of bis(μ-ethylideneamido)-bis(tricarbonyliron)(Fe–Fe)

Cited by 16 publications

References 6 publications

Reaction of Fe₃(CO)₁₂ with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

Reaction of Fe₃(CO)₁₂ with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

Unusual Reactions of Cationic Bridging Carbyne Complexes of Bis(η⁵-cyclopentadienyl)diiron Tricarbonyl with Carbonylmetal Anions. A Route to Diiron Bridging Carbyne Complexes

Remarkable Reactions of Cyclooctatetraene Diiron‐Bridging Carbyne Complexes with Amino and Amido Compounds: Nucleophilic Addition to and Breaking of the Cyclooctatetraene Ring

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Structure of bis(μ-ethylideneamido)-bis(tricarbonyliron)(Fe–Fe)

Cited by 16 publications

References 6 publications

Reaction of Fe3(CO)12 with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

Reaction of Fe3(CO)12 with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

Unusual Reactions of Cationic Bridging Carbyne Complexes of Bis(η5-cyclopentadienyl)diiron Tricarbonyl with Carbonylmetal Anions. A Route to Diiron Bridging Carbyne Complexes

Remarkable Reactions of Cyclooctatetraene Diiron‐Bridging Carbyne Complexes with Amino and Amido Compounds: Nucleophilic Addition to and Breaking of the Cyclooctatetraene Ring

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Reaction of Fe₃(CO)₁₂ with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

Reaction of Fe₃(CO)₁₂ with TelluriumNitrogen Heterocycles: A Source of Novel Organoiron Compounds

Unusual Reactions of Cationic Bridging Carbyne Complexes of Bis(η⁵-cyclopentadienyl)diiron Tricarbonyl with Carbonylmetal Anions. A Route to Diiron Bridging Carbyne Complexes