Reaction of MoCl3(THF)3 with [Me2Si{NLi(Dipp)}2]2 (Dipp = 2,6-i-PrC6H3) afforded a triply bonded dimolybdenum complex 1,2-Mo2Cl2[Me2Si(NDipp)2]2 1, spanned by two Me2Si[N(Dipp)]2 ligands, thus resulting in a syn conformation. The air- and moisture-sensitive compound 1 was characterized by NMR spectroscopic, elemental, and single-crystal X-ray crystallographic analysis. Reduction of 1 by Na/Hg yielded the quadruply bonded dimeric complex Mo2[Me2Si(NDipp)2]2 2, which was also characterized by the aforementioned analytical methods. The Mo-Mo bond was determined to be 2.1784(12) A, which is considered a long quadruple bond. In addition, density functional theory (DFT) computations on compound 2 provided insight into the intriguing Mo-Mo quadruple bond.
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http://dx.doi.org/10.1021/ja0635884 | DOI Listing |
Chemphyschem
January 2025
Institut für Analytische Chemie, Universität Leipzig, 04103, Leipzig, Germany.
The red/green cyanobacteriochrome (CBCR) slr1393g3 exhibits a quantum yield of only 8 % for its forward photoconversion, significantly lower than other species from the same CBCR subfamily. The cause for this reduced photoconversion is not yet clear, although in the related NpR6012g4 dark-state structural heterogeneity of a paramount Trp residue has been proposed to cause the formation of nonproductive subpopulation. However, there is no such information on the equivalent residue in slr1393g3, W496.
View Article and Find Full Text PDFInorg Chem
August 2024
School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
Dalton Trans
February 2024
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
In an effort to explore the coordination chemistry of the coordinative sulfur centers in -ruthenaborane [(Cp*Ru)(BH)(CSH)] (-1), we have thermolyzed -1 with group-6 metal carbonyls [M(CO)·THF] (M = Cr, Mo and W). The reaction of -1 with [Cr(CO)·THF] resulted in the formation of hetero-trimetallic triply bridging borylene [(Cp*Ru)(μ-CO)(μ-CHS-κS':κS''){Cr(CO)}(μ-BH)] (2), bridging boryl-borylene [(Cp*Ru)(μ-CO){(μ-BH(CHS)-κB:κS':κS'')}{Cr(CO)}(μ-BH)] (3), and sulfido bridged hetero-trimetallic complex [(Cp*Ru)(μ-CO){Cr(CO)}(μ-S)] (4). In 2, one side of RuCr-triangle features a μ-BH ligand while the other side is quadruply bridged by a methanedithiolato ligand in an unsymmetrical fashion.
View Article and Find Full Text PDFChemistry
March 2024
State Key Laboratory of Materials-Oriented Chemical Engineering, School of Chemistry and Molecular Engineering, Nanjing Tech University, 211816, Nanjing, China.
Quantum chemical calculations of the anions AeF (Ae=Be-Ba) have been carried out using ab initio methods at the CCSD(T)/def2-TZVPP level and density functional theory employing BP86 with various basis sets. The detailed bonding analyses using different charge- and energy partitioning methods show that the molecules possess three distinctively different dative bonds in the lighter species with Ae=Be, Mg and four dative bonds when Ae=Ca, Sr, Ba. The occupied 2p atomic orbitals (AOs) and to a lesser degree the occupied 2s AO of F donate electronic charge into the vacant sp(σ) and p(π) orbitals of Be and Mg which leads to a triple bond Ae F.
View Article and Find Full Text PDFChemistry
April 2024
School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.
Supramolecular polymers offer tremendous potential to produce new "smart" materials, however, there remains a need to develop systems that are responsive to external stimuli. In this work, visible-light responsive hydrogen-bonded supramolecular polymers comprising photoresponsive supramolecular synthons (I-III) consisting of two hydrogen bonding motifs (HBMs) connected by a central ortho-tetrafluorinated azobenzene have been characterized by DOSY NMR and viscometry. Comparison of different hydrogen-bonding motifs reveals that assembly in the low and high concentration regimes is strongly influenced by the strength of association between the HBMs.
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