199620-14-9Relevant articles and documents
Transition metal complexes of chromium, molybdenum, tungsten, and manganese containing η1(S)-2,5-dimethylthiophene, benzothiophene, and dibenzothiophene ligands
Reynolds, Michael A.,Guzei, Ilia A.,Logsdon, Bradley C.,Thomas, Leonard M.,Jacobson, Robert A.,Angelici, Robert J.
, p. 4075 - 4081 (1999)
Ultraviolet photolysis of hexanes solutions containing the complexes M(CO)6 (M = Cr, Mo, W) or CpMn(CO)3 (Cp = η5-C5H5) and excess thiophene (T*) (T* = 2,5-dimethylthiophene (2,5-Me2T), benzothiophene (BT), or dibenzothiophene (DBT)) produces the η1(S)-T* complexes (CO)5M(η1(S)-T*) 1-8 or Cp(CO)2Mn(η1(S)-T*) 9-11, respectively. However, when T* = DBT and M = Mo, a mixture of two products results, which includes (CO)5Mo(η1(S)-DBT), 4a, and the π-complex (CO)3Mo(η6-DBT), 4b, as detected by 1H NMR spectroscopy. Only the complexes (CO)5W(η1(S)-DBT) (1), (CO)5Cr(η1(S)-DBT) (5), and Cp(CO)2Mn(η1(S)-DBT) (9) were sufficiently stable (several days) to be isolated and characterized by elemental analyses. Rates of DBT ligand displacement by CO (1 atm) at room temperature decreased in the order 5 > 1 > 9. Single-crystal, X-ray structural determinations are reported for 1, 5, and 9. The tilt angle (θ) of the DBT ligand in these and related complexes is discussed in terms of π-back-bonding to the DBT ligand.
Chromium-manganese selenide carbonyl complexes: Paramagnetic clusters and relevance to C = O activation of acetone
Shieh, Minghuey,Lin, Chien-Nan,Miu, Chia-Yeh,Hsu, Miao-Hsing,Pan, Yi-Wen,Ho, Li-Fang
, p. 8056 - 8066 (2011/01/10)
The paramagnetic even-electron cluster, [Et4N] 2[Se2Cr3(CO)10], was found to react readily with Mn(CO)5Br in acetone to produce two unprecedented mixed chromium-manganese selenide carbonyl complexes, [Et4N][Me 2CSe2{Mn(CO)4}{Cr(CO)5} 2] ([Et4N][1]) and [Et4N]2[Se 2Mn3(CO)10{Cr(CO)5}2] ([Et4N]2[2]). X-ray crystallographic analysis showed that anion 1 consisted of two Se-Cr(CO)5 moieties, which were further bridged by one isopropylene group and one Mn(CO)4 moiety. The dianionic cluster 2 was shown to display a Se2Mn3 square-pyramidal core with each Se atom externally coordinated by one Cr(CO)5 group. The formation of complex 1, presumably via C=O activation of acetone, was further facilitated by acidification of the reaction of [Et4N]2[Se2Cr3(CO)10] with Mn(CO)5Br in acetone. Complex 1 readily transformed into 2 upon treatment with Mn2(CO)10 in a KOH/MeOH/MeCN solution. Cluster 2 was a 51-electron species, which readily converted to the known 49-electron cluster [Se2Mn3(CO)9]2- upon heating and bubbling with CO. Magnetic studies of the even-electron cluster, [Et4N]2[Se2Cr3(CO) 10], and the odd-electron species, [Et4N]2[2] and [PPN]2[Se2Mn3(CO)9], were determined by the SQUID measurement to have 2, 3, and 1 unpaired electrons, respectively. In addition, the nature and formation of complexes 1 and 2 are discussed, and the magnetic properties and electrochemistry of [Se 2Cr3(CO)10]2-, 2, and [Se 2Mn3(CO)9]2- were further studied and elucidated by molecular orbital calculations at the PW91 level of density functional theory.
Diversity and design of metal-based carbon monoxide-releasing molecules (CO-RMs) in aqueous systems: Revealing the essential trends
Zhang, Wei-Qiang,Atkin, Anthony J.,Thatcher, Robert J.,Whitwood, Adrian C.,Fairlamb, Ian J. S.,Lynam, Jason M.
, p. 4351 - 4358 (2009/10/17)
The CO-releasing ability of a diverse library of primary metal carbonyl complexes has been assessed using a deoxymyoglobin-carbonmonoxymyglobin assay. A wide spectrum of rates for the CO-release process was observed in aqueous systems. For octahedral dsu
