4-(Dimethylamino)pyridinium trichlorido[4-(dimethylamino)pyridine-κN]cobaltate(II)

Abstract

Key indicators: single-crystal X-ray study; T = 293 K; mean (C-C) = 0.002 Å; R factor = 0.021; wR factor = 0.054; data-to-parameter ratio = 16.2.In the anion of the title compound, (C 7 H 11 N 2 )[CoCl 3 -(C 7 H 10 N 2 )], the Co II ion is coordinated by one N atom from a 4-(dimethylamino)pyridine (DMAP) ligand and three Cl atoms, forming a CoNCl 3 polyhedron with a distorted tetrahedral geometry. In the crystal, cations and anions are linked via weak N-HÁ Á ÁCl and C-HÁ Á ÁCl hydrogen bonds. Double layers of complex anions stack along the b-axis direction, which alternate with double layers of 4-(dimethylamino)-pyridinium cations. Related literature Data collectionBruker APEXII diffractometer 7932 measured reflections 3230 independent reflections 2982 reflections with I > 2(I) R int = 0.012

Synthesis of (POCOP)Co(Ph)(X) Pincer Complexes and Observation of Aryl–Aryl Reductive Elimination Involving the Pincer Aryl

“…In addition, the stronger preference of POCOP for a square-planar over tetrahedral geometry should further stabilize the low-spin geometry. Indeed, Co­(II) complexes of similar aryl/bis­(phosphine) type 5,5-pincers have also been reported to be low-spin, square-planar compounds. , …”

“…This solid was collected, and single crystals suitable for X-ray diffraction were grown from a concentrated acetonitrile solution. The structure was determined to be [(DMAP)­H]­[(DMAP)­CoCl 3 ] with a unit cell matching that previously reported .…”

“…The structure was determined to be [(DMAP)H][(DMAP)CoCl 3 ] with a unit cell matching that previously reported. 49 A-1 is most closely related to (POCOP tBu )CoI reported by Goldberg, Heinekey, and coworkers. 50 A few differently substituted (POCOP)Co(CO) n (n = 1 or 2) complexes were very recently disclosed by Guan et al 51 The 1 H nuclear magnetic resonance (NMR) spectrum of A-1 displayed four broad, strongly contact-shifted signals with integral ratios of 24:4:2:1, consistent with formation of a paramagnetic Co II complex.…”

“…49,54 A-1 readily served as a starting material for the synthesis of derivative (POCOP)CoX complexes. Treatment of solutions of A-1 with Me 3 Si-X (X = Br, I, or OTf) resulted in rapid and clean formation of (POCOP)Co(Br) (A-2), (POCOP)Co(I) (A-3), and (POCOP)Co(OTf) (A-4) (Figure3).Reaction of A-1 with NaO t Bu, MeLi, and PhLi resulted in the formation of (POCOP)Co(O t Bu) (A-5), (POCOP)Co-(Me) (A-6), and (POCOP)Co(Ph) (A-7), respectively.…”

Selective Synthesis and Thermodynamic Relations of Polymorphic Co(NCS)2‐4‐Dimethylaminopyridine Coordination Compounds

“…It is noted, that no crystal structures with Co(NCS) 2 and DMAP are reported in the CCDC database but some discrete complexes with other transition metal cations are known . However, for compounds with other anions in which Co is coordinated by DMAP, more octahedral than tetrahedral compounds are known . It is also noted that a 1 D compound is reported, in which Co cations are linked by pairs of azido ligands into chains, an arrangement that exactly corresponds to that what we expected for thiocyanate coordination polymers and which indicates that also with Co(NCS) 2 the desired chain compound might be available .…”