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
The production of olefins via on‐purpose dehydrogenation of alkanes allows for a more efficient, selective and lower cost alternative to processes such as steam cracking. Silica‐supported pincer‐iridium complexes of the form [(≡SiO−R4POCOP)Ir(CO)] (R4POCOP=κ3‐C6H3‐2,6‐(OPR2)2) are effective for acceptorless alkane dehydrogenation, and have been shown stable up to 300 °C. However, while solution‐phase analogues of such species have demonstrated high regioselectivity for terminal olefin production under transfer dehydrogenation conditions at or below 240 °C, in open systems at 300 °C, regioselectivity under acceptorless dehydrogenation conditions is consistently low. In this work, complexes [(≡SiO−
- Award ID(s):
- 1705746
- PAR ID:
- 10236534
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemCatChem
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 1867-3880
- Page Range / eLocation ID:
- p. 407-415
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract 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. -
Our laboratory has reported that (CX3Phebox)Ir(H)(OAc) (X = H, F) catalysts are highly active for the acceptorless dehydrogenation of n-alkanes1, particularly in the presence of Lewis acids. In this work we report the synthesis of isoelectronic (Pybox)Os(H)(OAc) and (Pybox)Ru(H)(OAc), and investigation of these complexes for alkane dehydrogenation. DFT calculations predict (Pybox)Ru(H)(OAc) to catalyze acceptorless alkane dehydrogenation with a barrier lower than that for (CH3Phebox)Ir(H)(OAc), while the barrier calculated for (Pybox)Os(H)(OAc) is even lower. The rate-limiting step chem. for the catalytic cycle is calculated to be a net M-H/C-H σ-bond metathesis reaction, although expulsion of H2 from the reaction mixture was found to be rate-determining under typical conditions for acceptorless n-alkane dehydrogenation catalyzed by (CF3Phebox)Ir(H)(OAc). H/D exchange experiments were used to probe the kinetics of C-H activation yielding the order of activity: (Pybox)Os(H)(OAc) > (Pybox)Ru(H)(OAc) > (CF3Phebox)Ir(H)(OAc). Exptl. investigation of catalysis by (Pybox)Ru(H)(OAc) and (Pybox)Os(H)(OAc) is still in progress but the Ru complex, unfortunately, does not appear to be stable at the high temperatures required for acceptorless alkane dehydrogenation. We have also reported that (CH3Phebox)Ir(C2H4)2 catalyzes selective dehydrogenative coupling of ethylene to butadiene via an iridacyclopentane complex.2 In this work we used the precursor (Pybox)OsH4 to investigate the same catalytic reaction and appears to result in and analogous dehydrogenative coupling of ethylene to form butadiene via an osmacyclopentane.more » « less
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We report the synthesis of molybdenum and tungsten bromo dicarbonyl complexes (POCOPtBu)MIIBr(CO)2(M = Mo or W; POCOPtBu = κ3-C6H3-1,3-[OP( tBu)2]2) supported by an anionic PCP pincer ligand, and the chromium complex (PNPtBu)Cr0(CO)3(PNPtBu = 2,6-bis(di- tert-butyl-phosphinomethyl)pyridine) bearing a neutral PNP pincer scaffold. The three group six complexes described in this study have been characterized by Liquid Injection Field Desorption Ionization Mass Spectrometry (LIFDI-MS), NMR, and IR spectroscopy. Single crystal X-ray diffraction studies show the MoIIand WIIcomplexes adopt a six-coordinate distorted trigonal prismatic geometry, whereas the Cr0complex exhibits a distorted octahedral geometry.
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Abstract A low‐spin and mononuclear vanadium complex, (Menacnac)V(CO)(η2‐P≡C
t Bu) (2 ) (Menacnac−=[ArNC(CH3)]2CH, Ar=2,6‐i Pr2C6H3), was prepared upon treatment of the vanadium neopentylidyne complex (Menacnac)V≡Ct Bu(OTf) (1 ) with Na(OCP)(diox)2.5(diox=1,4‐dioxane), while the isoelectronic ate‐complex [Na(15‐crown‐5)]{([ArNC(CH2)]CH[C(CH3)NAr])V(CO)(η2‐P≡Ct Bu)} (4 ), was obtained via the reaction of Na(OCP)(diox)2.5and ([ArNC(CH2)]CH[C(CH3)NAr])V≡Ct Bu(OEt2) (3 ) in the presence of crown‐ether. Computational studies suggest that the P‐atom transfer proceeds by [2+2]‐cycloaddition of the P≡C bond across the V≡Ct Bu moiety, followed by a reductive decarbonylation to form the V−C≡O linkage. The nature of the electronic ground state in diamagnetic complexes,2 and4 , was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X‐ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X‐ray single‐crystal structural characterization. In combination, these data are consistent with a low‐valent vanadium ion in complexes2 and4 . This study represents the first example of a metathesis reaction between the P‐atom of [PCO]−and an alkylidyne ligand. -
Abstract A low‐spin and mononuclear vanadium complex, (Menacnac)V(CO)(η2‐P≡C
t Bu) (2 ) (Menacnac−=[ArNC(CH3)]2CH, Ar=2,6‐i Pr2C6H3), was prepared upon treatment of the vanadium neopentylidyne complex (Menacnac)V≡Ct Bu(OTf) (1 ) with Na(OCP)(diox)2.5(diox=1,4‐dioxane), while the isoelectronic ate‐complex [Na(15‐crown‐5)]{([ArNC(CH2)]CH[C(CH3)NAr])V(CO)(η2‐P≡Ct Bu)} (4 ), was obtained via the reaction of Na(OCP)(diox)2.5and ([ArNC(CH2)]CH[C(CH3)NAr])V≡Ct Bu(OEt2) (3 ) in the presence of crown‐ether. Computational studies suggest that the P‐atom transfer proceeds by [2+2]‐cycloaddition of the P≡C bond across the V≡Ct Bu moiety, followed by a reductive decarbonylation to form the V−C≡O linkage. The nature of the electronic ground state in diamagnetic complexes,2 and4 , was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X‐ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X‐ray single‐crystal structural characterization. In combination, these data are consistent with a low‐valent vanadium ion in complexes2 and4 . This study represents the first example of a metathesis reaction between the P‐atom of [PCO]−and an alkylidyne ligand.