Übergangsmetall‐Carbin‐Komplexe, LXVIII. Synthese und Struktur neuartiger zweikerniger Biscarbin‐Komplexe des Chroms, Molybdäns und Wolframs mit verbrückenden Phenylthio‐, Arylseleno‐, Halogeno‐ und Pseudohalogeno‐Liganden

Fischer, Ernst Otto; Wittmann, Dieter; Himmelreich, Dieter; Cai, Rui; Ackermann, Kathrin; Neugebauer, Dietmar

doi:10.1002/cber.19821150920

Cited by 35 publications

(8 citation statements)

References 17 publications

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“…An experimental example of each type is shown in Figure a,b, respectively. The latter is in fact the most common case with 363 structures, including, on the one hand, more or less complex ligands in which the interacting donor group can be an ester (137 hits), a ketone (87 hits), or an amide (34 hits), although other examples are found for ligands with less abundant carbonyl-containing motives such as aldehydes (BAMXAO, EGOJAM), carboxylic acids (IFUCIV, KACBEX), thioesters (FIHYUQ, FISMOK), isocyanates (BITKOE), azodicarboxylates (CARLUC), ureates (MURFEC), maleic anhydrides (POVZAB), and nucleic acids derivatives (ELIWEC) . On the other hand, there are only 22 structures in which the donor carbonyl is found in an independent organic molecule (19 (CH 3 ) 2 CO, 2 (C 6 H 5 ) 2 CO, 1 tBu–COOH).…”

Section: Resultssupporting

confidence: 64%

Intermolecular Carbonyl···Carbonyl Interactions in Transition-Metal Complexes

Echeverría

2018

Inorg. Chem.

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We performed a comprehensive analysis of intermolecular carbonyl-carbonyl interactions in transition-metal complexes. Those interactions can be classified in two main types depending on the organometallic or organic nature of the donor carbonyl: M-CO···CO and R-CO···CO, respectively. By means of a combined structural and computational study we unraveled their geometrical features and strength. Moreover, electronic structure, natural bond orbitals, energy decomposition analysis, and quantum theory of atoms in molecules calculations were performed to try to understand their nature. Remarkably, we discovered that these carbonyl-carbonyl contacts have several features of the n → π* interaction. The charge transfer from an oxygen lone pair to an empty antibonding π orbital of the acceptor carbonyl is also accompanied by an electrostatic O···C interaction. To the best of our knowledge this is the first report of an intermolecular n → π* interaction in metal complexes. These results might be significant, for instance, for the catalytic activation of carbonyl-containing small molecules with metal compounds or in the design of hybrid organic-inorganic materials, metal-organic frameworks, and other extended structures.

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Section: Resultssupporting

confidence: 64%

Intermolecular Carbonyl···Carbonyl Interactions in Transition-Metal Complexes

Echeverría

2018

Inorg. Chem.

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“…These structural features indicate that the cation in 4a can be best regarded as being composed of (η 5 -cyclopentadienyl)Mo(CO) 3 and (η 7 -cycloheptatrienyl)Mo(CO) 2 moieties which are additionally linked by a μ-iodo ligand. The Mo−I−Mo angles in molecules A and B are 104.56(2) and 105.22(2)°, respectively, and are similar to those of other iodine-bridged species, , for which a relatively wide range of angles has been observed due to the general structural flexibility of halide bridges. Although the formation of the doubly bridged complexes 4 from precursors 3 might give the impression that the (η 5 -cyclopentadienyl)Mo(CO) 3 I unit should be regarded as a hemilabile donor group only weakly coordinating to the (η 7 -cycloheptatrienyl)Mo(CO) 2 fragment, this is not reflected by the molybdenum−iodine distances, as the newly formed I−Mo(CO) 2 bond is even shorter than the preexisting (CO) 3 Mo−I bond (2.8196(7) vs 2.8510(7) Å in molecule A and 2.8158(7) vs 2.8572(7) Å in molecule B).…”

Section: Resultssupporting

confidence: 60%

Synthesis and Reactivity of Doubly Bridged μ-η⁵:η⁷-Cyclopentadienylcycloheptatrienyl Dimolybdenum Complexes

Tamm¹,

Baum²,

and³

et al. 2001

Organometallics

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The reaction of tropylium tetrafluoroborate, (C7H7)BF4, with lithium cyclopentadienides afforded isomeric mixtures of dihydrosesquifulvalenes ((1,3,5-cycloheptatrien-7-yl)cyclopentadienes) of the type C5H3RR‘−C7H7 (1a, R = R‘ = tert-butyl; 1b, R = tert-butyl, R‘ = H; 1c, R = R‘ = H). Lithiation of the hydrocarbons 1a−c followed by reaction with [(CH3CN)3Mo(CO)3], oxidation with iodine, and hydride abstraction using triphenylcarbenium tetrafluoroborate, (Ph3C)BF4, resulted in the formation of the intensely colored sesquifulvalene complexes [(η5-2,4-t-Bu2C5H2−C7H6)Mo(CO)3I]BF4 (2a), [(η5-3-t-BuC5H3−C7H6)Mo(CO)3I]BF4 (2b), and [(η5-C5H4−C7H6)Mo(CO)3I]BF4 (2c). Because of the poor solubility and stability of 2c, the arene exchange reaction with [(η6-p-xylene)Mo(CO)3] and complexation of the cycloheptatrienyl moiety could only be carried out with 2a,b, giving bimetallic [(μ-η5:η7-2,4-t-Bu2C5H2−C7H6)Mo2(CO)6I]BF4 (3a) and [(μ-η5:η7-3-t-BuC5H3−C7H6)Mo2(CO)6I]BF4 (3b), in which the five- and seven-membered rings are coordinated in η5 and η7 modes, respectively. 3a,b were thermally converted into syn-facial [(μ-η5:η7-2,4-t-Bu2C5H2−C7H6)Mo2(CO)5(μ-I)]BF4 (4a) and [(μ-η5:η7-3-t-BuC5H3−C7H6)Mo2(CO)5(μ-I)]BF4 (4b) by intramolecular CO substitution and formation of an additional Mo−I−Mo bridge. Reaction with triphenylphosphine lead to cleavage of the newly formed Mo−I bond and addition to the dicarbonylcycloheptatrienylmolybdenum unit to yield [(μ-η5:η7-2,4-t-Bu2C5H2−C7H6)Mo2(CO)5I(PPh3)]BF4 (5a) and [(μ-η5:η7-3-t-BuC5H3−C7H6)Mo2(CO)5I(PPh3)]BF4 (5b). Similarly, addition of NaI to 4a gave neutrally charged [(μ-η5:η7-2,4-t-Bu2C5H2−C7H6)Mo2(CO)5I2] (5). In addition, the dihydrosesquifulvalene 1a has been employed in the syntheses of the methyl derivatives [(μ-η5:η7-2,4-t-Bu2C5H2−C7H6)Mo(CO)3(CH3)]BF4 (8) and [(μ-η5:η7-2,4-t-Bu2C5H2−C7H6)Mo2(CO)6(CH3)]BF4 (9) following a protocol similar to that described for complexes 2 and 3. Attempts to convert 9 into a methyl-bridged complex via addition of NaI and Ag(CF3SO3) unexpectedly gave the corresponding triflate [(μ-η5:η7-2,4-t-Bu2C5H2−C7H6)Mo2(CO)6(CH3)]CF3SO3 (10) only. The X-ray crystal structures of 4a·CH2Cl2, 5a·CH2Cl2, and 10·CH2Cl2 are reported. Attempts to obtain sesquifulvalene complexes containing Mo−Mo bonds proved to be unsuccessful.

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“…For the aminocarbyne ligand, the Mo−C−N linkage is essentially linear (176.8(3)°). The short Mo−C distance at 1.808(4) Å is diagnostic of the Mo−C multiple bonding, which is comparable to those in the other carbyne complexes,16a e.g., [Mo(⋮CNEt 2 )(CO) 3 (μ-I)] 2 (1.80(2) Å) and [CpMo(⋮CCH 2 CMe 3 )(P(OMe) 3 ) 2 ] (1.796(2) Å; Cp = η 5 -C 5 H 5 ) . The bond angles around the N atom (125.3(4)°, 126°, and 108°) are indicative of its sp 2 character, which is consistent with the C(1)−N bond length at 1.345(5) Å, being much shorter than the typical C−N single bond distance of 1.47 Å.…”

Section: Resultsmentioning

confidence: 53%

Protonation and Methylation of Zerovalent Molybdenum Complexes of the Types trans-[Mo(CNR)(L)(Ph₂PCH₂CH₂PPh₂)₂] (R = Ph or Buⁿ; L = N₂, CO, or Nitrile) and trans-[Mo(CO)(L‘)(Ph₂PCH₂CH₂PPh₂)₂] (L‘ = N₂ or Nitrile) To Give Carbyne or Hydrido Complexes¹

et al. 2000

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Treatment of trans-[Mo(CNPh)(N 2 )(dppe) 2 ] with aqueous HBF 4 afforded an aminocarbyne complex, which was isolated as trans-[Mo(tCNHPh)(OdCMe 2 )(dppe) 2 ][BF 4 ] (7) after crystallization of the crude product from acetone-hexane, whereas the reaction of trans-[Mo-and cis-[Mo(tCNHR)(CO)(dppe) 2 ][BF 4 ] (10). In solution at room temperature, the latter complexes gradually isomerized to the hydrido complexes [MoH(CNR)(CO)(dppe) 2 ][BF 4 ] (12). Related aminocarbyne complexes cis-[Mo(tCNMeR)(CO)(dppe) 2 ][BF 4 ] (13) were obtained from the reactions of 4 with [Me 3 O][BF 4 ]. For comparison, carbonyl complexes trans-[Mo-(CO)(N 2 )(dppe) 2 ] and trans-[Mo(CO)(p-MeOC 6 H 4 CN)(dppe) 2 ] were allowed to react with aqueous HBF 4 , which revealed the formation of the hydrido complexes [MoH(CO)(H 2 O)-(dppe) 2 ][BF 4 ] (14) and [MoH(CO)(p-MeOC 6 H 4 CN)(dppe) 2 ][BF 4 ] (15), respectively. The X-ray analyses were undertaken to determine the detailed structures for 7, 10a (R ) Ph), 12a (R ) Ph), 13b (R ) Bu n ), 14‚THF, and 15‚Et 2 O.

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Übergangsmetall‐Carbin‐Komplexe, LXVIII. Synthese und Struktur neuartiger zweikerniger Biscarbin‐Komplexe des Chroms, Molybdäns und Wolframs mit verbrückenden Phenylthio‐, Arylseleno‐, Halogeno‐ und Pseudohalogeno‐Liganden

Cited by 35 publications

References 17 publications

Intermolecular Carbonyl···Carbonyl Interactions in Transition-Metal Complexes

Intermolecular Carbonyl···Carbonyl Interactions in Transition-Metal Complexes

Synthesis and Reactivity of Doubly Bridged μ-η⁵:η⁷-Cyclopentadienylcycloheptatrienyl Dimolybdenum Complexes

Protonation and Methylation of Zerovalent Molybdenum Complexes of the Types trans-[Mo(CNR)(L)(Ph₂PCH₂CH₂PPh₂)₂] (R = Ph or Buⁿ; L = N₂, CO, or Nitrile) and trans-[Mo(CO)(L‘)(Ph₂PCH₂CH₂PPh₂)₂] (L‘ = N₂ or Nitrile) To Give Carbyne or Hydrido Complexes¹

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Übergangsmetall‐Carbin‐Komplexe, LXVIII. Synthese und Struktur neuartiger zweikerniger Biscarbin‐Komplexe des Chroms, Molybdäns und Wolframs mit verbrückenden Phenylthio‐, Arylseleno‐, Halogeno‐ und Pseudohalogeno‐Liganden

Cited by 35 publications

References 17 publications

Intermolecular Carbonyl···Carbonyl Interactions in Transition-Metal Complexes

Intermolecular Carbonyl···Carbonyl Interactions in Transition-Metal Complexes

Synthesis and Reactivity of Doubly Bridged μ-η5:η7-Cyclopentadienylcycloheptatrienyl Dimolybdenum Complexes

Protonation and Methylation of Zerovalent Molybdenum Complexes of the Types trans-[Mo(CNR)(L)(Ph2PCH2CH2PPh2)2] (R = Ph or Bun; L = N2, CO, or Nitrile) and trans-[Mo(CO)(L‘)(Ph2PCH2CH2PPh2)2] (L‘ = N2 or Nitrile) To Give Carbyne or Hydrido Complexes1

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Synthesis and Reactivity of Doubly Bridged μ-η⁵:η⁷-Cyclopentadienylcycloheptatrienyl Dimolybdenum Complexes

Protonation and Methylation of Zerovalent Molybdenum Complexes of the Types trans-[Mo(CNR)(L)(Ph₂PCH₂CH₂PPh₂)₂] (R = Ph or Buⁿ; L = N₂, CO, or Nitrile) and trans-[Mo(CO)(L‘)(Ph₂PCH₂CH₂PPh₂)₂] (L‘ = N₂ or Nitrile) To Give Carbyne or Hydrido Complexes¹