By varying the halogen-bond-donor molecule, 11 new halogen-bonding cocrystals involving thiourea or 1,3-dimethylthiourea were obtained, namely, 1,3-dimethylthiourea–1,2-diiodo-3,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 1 , thiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·CH 4 N 2 S, 2 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 3 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–methanol (1/1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S·CH 4 O, 4 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–ethanol (1/1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S·C 2 H 6 O, 5 , 1,3-dimethylthiourea–1,4-diiodo-2,3,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 6 , 1,3-dimethylthiourea–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 3 H 8 N 2 S, 7 , 1,3-dimethylthiourea–1,1,2,2-tetraiodoethene (1/1), C 6 H 16 N 4 S 2 ·C 2 I 4 , 8 , [(dimethylamino)methylidene](1,2,2-triiodoethenyl)sulfonium iodide–1,1,2,2-tetraiodoethene–acetone (1/1/1), C 5 H 8 I 3 N 2 S + ·I − ·C 3 H 6 O·C 2 I 4 , 9 , 2-amino-4-methyl-1,3-thiazol-3-ium iodide–1,1,2,2-tetraiodoethene (2/3), 2C 4 H 7 N 2 S + ·2I − ·3C 2 I 4 ,more »
POCOP-type cobalt and nickel pincer complexes bearing an appended phosphinite group
The reaction of 1,3,5-( i Pr 2 PO) 3 C 6 H 3 with Co 2 (CO) 8 leads to the isolation of a POCOP-type mononuclear pincer complex {κ P ,κ C ,κ P -2,4,6-( i Pr 2 PO) 3 C 6 H 2 }Co(CO) 2 (1) or a tetranuclear species {κ P -{κ P ,κ C ,κ P -2,4,6-( i Pr 2 PO) 3 C 6 H 2 }Co(CO) 2 } 2 Co 2 (CO) 6 (2), depending on the ligand to cobalt ratio employed. The latter compound can be an impurity during the synthesis of {2,6-( i Pr 2 PO) 2 -4-Me 2 N-C 6 H 2 }Co(CO) 2 , when the ligand precursor 5-(dimethylamino)resorcinol is contaminated with phloroglucinol due to incomplete monoamination. Similarly, the reaction of 1,3,5-( i Pr 2 PO) 3 C 6 H 3 with NiCl 2 in the presence of 4-dimethylaminopyridine provides {κ P ,κ C ,κ P -2,4,6-( i Pr 2 PO) 3 C 6 H 2 }NiCl (3) bearing an appended phosphinite group. Structures 1–3 have been studied by X-ray crystallography.
- Award ID(s):
- 1800151
- Publication Date:
- NSF-PAR ID:
- 10187242
- Journal Name:
- Canadian Journal of Chemistry
- Page Range or eLocation-ID:
- 1 to 7
- ISSN:
- 0008-4042
- Sponsoring Org:
- National Science Foundation
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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. -
The title compound, bis(1,2-diphenyl-2-sulfanylideneethanethiolato-κ 2 S , S ′)(1,3,5-triaza-7-phosphaadamantane-κ P )cobalt(II) dichloromethane hemisolvate, [Co(pdt) 2 (PTA)]·0.5C 2 H 4 Cl 2 or [Co(C 14 H 10 S 2 ) 2 (C 6 H 12 N 3 P)]·0.5C 2 H 4 Cl 2 , contains two phenyldithiolene (pdt) ligands and a 1,3,5-triaza-7-phosphaadamantane (PTA) ligand bound to cobalt with the solvent 1,2-dichloroethane molecule located on an inversion center. The cobalt core exhibits an approximately square-pyramidal geometry with partially reduced thienyl radical monoanionic ligands. The supramolecular network is consolidated by hydrogen-bonding interactions primarily with nitrogen, sulfur and chlorine atoms, as well as parallel displaced π-stacking of the aryl rings. The UV–vis, IR, and CV data are also consistent with monoanionic dithiolene ligands and an overall Co II oxidation state.
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Boron monofluoride (BF) is a diatomic molecule with 10 valence electrons, isoelectronic to carbon monoxide (CO). Unlike CO, which is a stable molecule at room temperature and readily serves as both a bridging and terminal ligand to transition metals, BF is unstable below 1800°C in the gas phase, and its coordination chemistry is substantially limited. Here, we report the isolation of the iron complex Fe(BF)(CO) 2 (CNAr Tripp2 ) 2 [Ar Tripp2 , 2,6-(2,4,6-( i- Pr) 3 C 6 H 2 ] 2 C 6 H 3 ; i -Pr, iso -propyl], featuring a terminal BF ligand. Single-crystal x-ray diffraction as well as nuclear magnetic resonance, infrared, and Mössbauer spectroscopic studies on Fe(BF)(CO) 2 (CNAr Tripp2 ) 2 and the isoelectronic dinitrogen (N 2 ) and CO complexes Fe(N 2 )(CO) 2 (CNAr Tripp2 ) 2 and Fe(CO) 3 (CNAr Tripp2 ) 2 demonstrate that the terminal BF ligand possesses particularly strong σ-donor and π-acceptor properties. Density functional theory and electron-density topology calculations support this conclusion.
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Accepted Manuscript1.0
- Publisher's Version of Record
- https://doi.org/10.1139/cjc-2020-0137
