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1. Octahedral iron( iv )–tosylimido complexes exhibiting single electron-oxidation reactivity

   https://doi.org/10.1039/C9SC02526J  

   Sabenya, Gerard ; Gamba, Ilaria ; Gómez, Laura ; Clémancey, Martin ; Frisch, Jonathan R. ; Klinker, Eric J. ; Blondin, Geneviève ; Torelli, Stéphane ; Que, Lawrence ; Martin-Diaconescu, Vlad ; et al ( October 2019 , Chemical Science)

   High valent iron species are very reactive molecules involved in oxidation reactions of relevance to biology and chemical synthesis. Herein we describe iron( iv )–tosylimido complexes [Fe IV (NTs)(MePy 2 tacn)](OTf) 2 ( 1(IV)NTs ) and [Fe IV (NTs)(Me 2 (CHPy 2 )tacn)](OTf) 2 ( 2(IV)NTs ), (MePy 2 tacn = N -methyl- N , N -bis(2-picolyl)-1,4,7-triazacyclononane, and Me 2 (CHPy 2 )tacn = 1-(di(2-pyridyl)methyl)-4,7-dimethyl-1,4,7-triazacyclononane, Ts = Tosyl). 1(IV)NTs and 2(IV)NTs are rare examples of octahedral iron( iv )–imido complexes and are isoelectronic analogues of the recently described iron( iv )–oxo complexes [Fe IV (O)(L)] 2+ (L = MePy 2 tacn and Me 2 (CHPy 2 )tacn, respectively). 1(IV)NTs and 2(IV)NTs are metastable and have been spectroscopically characterized by HR-MS, UV-vis, 1 H-NMR, resonance Raman, Mössbauer, and X-ray absorption (XAS) spectroscopy as well as by DFT computational methods. Ferric complexes [Fe III (HNTs)(L)] 2+ , 1(III)–NHTs (L = MePy 2 tacn) and 2(III)–NHTs (L = Me 2 (CHPy 2 )tacn) have been isolated after the decay of 1(IV)NTs and 2(IV)NTs in solution, spectroscopically characterized, and the molecular structure of [Fe III (HNTs)(MePy 2 tacn)](SbF 6 ) 2 determined by single crystal X-ray diffraction. Reaction of 1(IV)NTs and 2(IV)NTs with different p -substituted thioanisoles results in the transfer of the tosylimido moiety to the sulphur atom producing sulfilimine products. In these reactions, 1(IV)NTs and 2(IV)NTs behave as single electron oxidants and Hammett analyses of reaction rates evidence that tosylimido transfer is more sensitive than oxo transfer to charge effects. In addition, reaction of 1(IV)NTs and 2(IV)NTs with hydrocarbons containing weak C–H bonds results in the formation of 1(III)–NHTs and 2(III)–NHTs respectively, along with the oxidized substrate. Kinetic analyses indicate that reactions proceed via a mechanistically unusual HAT reaction, where an association complex precedes hydrogen abstraction. 

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2. Synthesis and characterization of Ag( i ) and Au( i ) complexes with macrocyclic hybrid amine N-heterocyclic carbene ligands

   https://doi.org/10.1039/C7NJ04020B  

   Lu, Taotao ; Yang, Chu-Fan ; Steren, Carlos A. ; Fei, Fan ; Chen, Xue-Tai ; Xue, Zi-Ling ( January 2018 , New Journal of Chemistry)

   Four macrocyclic hybrid salts with different numbers of benzimidazolium and amine units, [H 2 L][PF 6 ] 2 (L = L 1 , L 2 , L 3 ) and [H 4 L 4 ][PF 6 ] 4 , have been employed as the heterocyclic carbene (NHC) precursors toward new Ag( i )– and Au( i )–NHC complexes. Three trinuclear and one tetranuclear Ag( i ) complexes 1–4 have been obtained from the reactions of the NHC precursors and Ag 2 O in acetonitrile. Four dinuclear Au( i )–NHC complexes 5–8 have been prepared by reacting the NHC precursors and AuCl(SMe 2 ) in the presence of NaOAc in DMF. The molecular structures of all the complexes are established by single-crystal X-ray diffraction studies. The metal ions in the Ag( i ) complexes 1–3 and the Au( i ) complexes 5–7 are coordinated with two macrocyclic NHC ligands to form a sandwiched structure. In contrast, a trinuclear Ag 3 core is located in the cavity of one macrocyclic ligand in [Ag 3 (L 4 )][PF 6 ] 3 ( 4 ). The photoluminescence properties of Au( i ) complexes 5–8 have also been investigated. 

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3. Synthesis, structures and luminescence properties of amine-bis(N-heterocyclic carbene) copper( i ) and silver( i ) complexes

   https://doi.org/10.1039/C8DT00599K  

   Lu, Taotao ; Wang, Jin-Yun ; Shi, Lin-Xi ; Chen, Zhong-Ning ; Chen, Xue-Tai ; Xue, Zi-Ling ( January 2018 , Dalton Transactions)

   A series of Ag( i ) and Cu( i ) complexes [Ag 3 (L 1 ) 2 ][PF 6 ] 3 ( 8 ), [Ag 3 (L 2 ) 2 ][PF 6 ] 3 ( 9 ), [Cu(L 1 )][PF 6 ] ( 10 ) and [Cu(L 2 )][PF 6 ] ( 11 ) have been synthesized by reactions of the tridentate amine-bis(N-heterocyclic carbene) ligand precursors [H 2 L 1 ][PF 6 ] 2 ( 6 ) and [H 2 L 2 ][PF 6 ] 2 ( 7 ) with Ag 2 O and Cu 2 O, respectively. Complexes 10 and 11 can also be obtained by transmetalation of 8 and 9 , respectively, with 3.0 equiv. of CuCl. A heterometallic Cu/Ag–NHC complex [Cu 2 Ag(L 1 ) 2 (CH 3 CN) 2 ][PF 6 ] 3 ( 12 ) is formed by the reaction of 8 with 2.0 equiv. of CuCl. All complexes have been characterized by NMR, electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction studies. The luminescence properties of 10–12 in solution and the solid state have been studied. At room temperature, 10–12 exhibit evident luminescence in solution and the solid state. The emission wavelengths are found to be identical at 483 nm in CH 3 CN, but they are 484, 480 and 592 nm in the solid state for 10–12 , respectively. These results suggest that 12 dissociates into two molecules of 10 and Ag( i ) ions in solution. Complex 12 is the first luminescent heterometallic Cu/Ag–NHC complex. 

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4. N 3 -Ligated nickel( ii ) diketonate complexes: synthesis, characterization and evaluation of O 2 reactivity

   https://doi.org/10.1039/d0dt01338b  

   Elsberg, Josiah G. ; Peterson, Austin ; Fuller, Amy L. ; Berreau, Lisa M. ( January 2020 , Dalton Transactions)

   Interest in O 2 -dependent aliphatic carbon–carbon (C–C) bond cleavage reactions of first row divalent metal diketonate complexes stems from the desire to further understand the reaction pathways of enzymes such as DKE1 and to extract information to develop applications in organic synthesis. A recent report of O 2 -dependent aliphatic C–C bond cleavage at ambient temperature in Ni( ii ) diketonate complexes supported by a tridentate nitrogen donor ligand [(MBBP)Ni(PhC(O)CHC(O)Ph)]Cl ( 7-Cl ; MBBP = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine) in the presence of NEt 3 spurred our interest in further examining the chemistry of such complexes. A series of new TERPY-ligated Ni( ii ) diketonate complexes of the general formula [(TERPY)Ni(R 2 -1,3-diketonate)]ClO 4 ( 1 : R = CH 3 ; 2 : R = C(CH 3 ) 3 ; 3 : R = Ph) was prepared under air and characterized using single crystal X-ray crystallography, elemental analysis, 1 H NMR, ESI-MS, FTIR, and UV-vis. Analysis of the reaction mixtures in which these complexes were generated using 1 H NMR and ESI-MS revealed the presence of both the desired diketonate complex and the bis-TERPY derivative [(TERPY) 2 Ni](ClO 4 ) 2 ( 4 ). Through selective crystallization 1–3 were isolated in analytically pure form. Analysis of reaction mixtures leading to the formation of the MBBP analogs [(MBBP)Ni(R 2 -1,3-diketonate)]X (X = ClO 4 : 5 : R = CH 3 ; 6 : R = C(CH 3 ) 3 ; 7-ClO4 : R = Ph; X = Cl: 7-Cl : R = Ph) using 1 H NMR and ESI-MS revealed the presence of [(MBBP) 2 Ni](ClO 4 ) 2 ( 8 ). Analysis of aerobic acetonitrile solutions of analytically pure 1–3 , 5 and 6 containing NEt 3 and in some cases H 2 O using 1 H NMR and UV-vis revealed evidence for the formation of additional bis-ligand complexes ( 4 and 8 ) but suggested no oxidative diketonate cleavage reactivity. Analysis of the organic products generated from 3 , 7-ClO4 and 7-Cl revealed unaltered dibenzoylmethane. Our results therefore indicate that N 3 -ligated Ni( ii ) complexes of unsubstituted diketonate ligands do not exhibit O 2 -dependent aliphatic C–C bond clevage at room temperature, including in the presence of NEt 3 and/or H 2 O. 

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5. Structure and magnetic characterization of some bicompartmental [N 6 O 2 ] divalent metal( ii ) complexes using bis(phenolato) ligands bearing two pendant bis(pyridyl) amine arms

   https://doi.org/10.1039/d3nj02380j  

   Mautner, Franz A. ; Fischer, Roland C. ; Torvisco, Ana ; Nakashima, Kai ; Handa, Makoto ; Mikuriya, Masahiro ; Salem, Nahed M. ; Overby, Gabriel J. ; Maier, Madison R. ; Louka, Febee R. ; et al ( August 2023 , New Journal of Chemistry)

   Reactions of the bicompartmental bis(phenolato) compound 6,6′-methylenebis(2-((bis(pyridin-2-ylmethyl)amino)methyl)-4-chlorophenol)hemihydrate (H 2 L ½H 2 O) with 3d metal( ii ) ions afforded novel fully structurally characterized bridged acetato dinuclear complexes [Mn 2 (HL)(μ 1,2 -OAc) 2 ]PF 6 (1) [Zn 2 (HL)(μ 1,2 -OAc)(H 2 O) 0.75 (MeOH) 0.25 ](PF 6 ) 2 ·0.45(H 2 O) (5) and [Cd 2 (HL)(μ 1,1,2 -OAc)(OAc)(H 2 O)]PF 6 ·H 2 O (6) as well as the polymeric bridged-azido tetranuclear catena -[Cu 4 (HL) 2 (μ 1,1 -N 3 ) 2 (μ 1,3 -N 3 ) 2 ](NO 3 ) 2 ·5H 2 O (4). The complex [Cu 4 (HL) 2 (ClO 4 ) 3 (H 2 O) 5 ](ClO 4 ) 3 ·5H 2 O (2) was partially characterized. In addition, three more dinuclear complexes [Cu 2 (H 2 L)(NO 3 ) 2 (H 2 O) 2 ](NO 3 ) 2 (3), [Cu 2 (HL)(OAc)(CH 3 OH)](PF 6 ) 2 (7) and [Cu 2 (HL)(NCS) 2 ]NO 3 ·2H 2 O (8) were also isolated. All complexes were characterized by CHN elemental analysis, IR and UV-Vis spectroscopy, ESI-MS, conductivity measurements and X-ray single crystal crystallography for compounds 1, 4, 5 and 6, where the bis(phenolato) ligand displayed different deprotonation (H 2 L, HL − and L 2− ). The magnetic susceptibility measurements over the temperature range 2–300 K revealed very weak antiferromagnetic coupling in dimanganese( ii ) 1 ( J = −1.64(1) cm −1 ) and almost negligible magnetic interaction in dicopper( ii ) 2 ( J = 0(3) cm −1 ). In the azido catena -[Cu 4 (HL) 2 (μ 1,1 -N 3 ) 2 (μ 1,3 -N 3 ) 2 ](NO 3 ) 2 ·5H 2 O (4) complex, the J value of −133(3) cm −1 was obtained upon moderate-to-strong antiferromagnetic coupling through the di-μ 1,3 -N 3 -bridged dicopper( ii ) unit with no magnetic interaction between the two copper( ii ) ions in the di-μ 1,1 -N 3 -bridged unit. 

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