- NSF-PAR ID:
- 10156790
- Date Published:
- Journal Name:
- Dalton Transactions
- ISSN:
- 1477-9226
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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.more » « less
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Abstract The syntheses of the 2,9‐dimesityl‐1,10‐phenanthroline (
dmesp ) metal complexes, [Cu(dmesp)(MeCN)]PF6(1 ), [Cu(dmesp)2]PF6(2 ), Fe(dmesp)Cl2(3 ), Co(dmesp)Cl2(4 ), Ni(dmesp)Cl2(5 ), Zn(dmesp)Cl2(6 ), Pd(dmesp)MeCl (7 ), Cu(dmesp)Cl (8 ), and Pd(dmesp)2Cl2(9 ), in good to high yields are described. These complexes were characterized by1H and13C NMR spectroscopy, HR–MS (ESI and/or APPI), and elemental analysis (CHN). The solid‐state structures of complexes1 –8 were determined by single‐crystal X‐ray analysis and their photophysical properties were also characterized. To demonstrate the versatility of this new platform, complexes3 –5 ,8 , and9 were employed in the catalytic oligomerization of ethylene using modified methyl aluminoxane (MMAO) as the cocatalyst, where Co(II) and Ni(II) complexes (4 and5 , respectively) were found to exhibit moderate selectivity for catalytic dimerization of ethylene to butenes over tri‐ or tetramerization. Complex8 is an effective catalyst of both the commonly encountered “click” reaction and amine arylation chemistries. Complexes6 and9 were found to be excellent catalysts for Friedel‐Crafts alkylation and Suzuki‐Miyaura coupling, respectively. -
Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh( iii ) devoid of agostic interactions. The complexes [X–Rh(κ 3 ( P,Si,Si )PhP( o -C 6 H 4 CH 2 Si i Pr 2 ) 2 ], where X = Cl (Rh-1), Br (Rh-2), I (Rh-3), OTf (Rh-4), Cl·GaCl 3 (Rh-5); derive from a bis(silyl)- o -tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl–Ir(κ 3 ( P,Si,Si )PhP( o -C 6 H 4 CH 2 Si i Pr 2 ) 2 ], Ir-1, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show that Rh-1 catalyzes effectively the dehydrogenative silylation of styrene with Et 3 SiH in toluene while it leads to hydrosilylation products in acetonitrile. Rh-1 is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et 3 SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers by Ir-1 renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M( iii ) complexes.more » « less
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Abstract A new series of mono‐ and bis‐alkynyl CoIII(TIM) complexes (TIM=2,3,9,10‐tetramethyl‐1,4,8,11‐tetraazacyclotetradeca‐1,3,8,10‐tetraene) is reported herein. The
trans ‐[Co(TIM)(C2R)Cl]+complexes were prepared from the reaction betweentrans ‐[Co(TIM)Cl2]PF6and HC2R (R=tri(isopropyl)silyl or TIPS (1 ), ‐C6H4‐4‐tBu (2 ), ‐C6H4‐4‐NO2(3 a ), andN ‐mesityl‐1,8‐naphthalimide or NAPMes(4 a )) in the presence of Et3N. The intermediate complexes of the typetrans ‐[Co(TIM)(C2R)(NCMe)](PF6)(OTf),3 b and4 b , were obtained by treating3 a and4 a , respectively, with AgOTf in CH3CN. Furthermore, bis‐alkynyltrans ‐[Co(TIM)(C2R)2]PF6complexes,3 c and4 c , were generated following a second dehydrohalogenation reaction between3 b and4 b , respectively, and the appropriate HC2R in the presence of Et3N. These new complexes have been characterized using X‐ray diffraction (2 ,3 a ,4 a , and4 c ), IR,1H NMR, UV/Vis spectroscopy, fluorescent spectroscopy (4 c ), and cyclic voltammetry.