Complexes trans-[MCl2(NCNMe2)2] (M = Pt 1, Pd 2) were cocrystallized with CHBr3 and CHI3, forming 1:2 adducts isomorphic with previously reported trans-[PtCl2(NCNMe2)2]·2CHI3. In all cases, the C–X···M (X = Br, I; M = Pd, Pt) metal-involving halogen bonding together with numerous chloride-halomethane halogen and hydrogen bonds were identified by single-crystal XRD experiments. Further DFT calculations and topological analysis of the electron density distribution within the framework of QTAIM method at the M06/DZP-DKH level of theory confirmed the existence of these interactions and their noncovalent nature. Estimated energies of such contacts vary from 1.6 to 3.1 kcal/mol.

The complexes trans-[PtCl 2 (NCNR 2 ) 2 ] (R 2 = Me 2 1, Et 2 2, (CH 2 ) 4 3) were cocrystallized with CBr 4 in CHCl 3 (1 and 3) or in MeNO 2 (2) forming adducts 1•CHCl 3 • CBr 4 , 2•2CBr 4 , and 3•2CBr 4 , respectively. In two out of three adducts, viz. 1•CHCl 3 •CBr 4 and 2•2CBr 4 , unique Br 3 C− Br•••η 2 (Cl−Pt) metal-involving bif urcated halogen bonding was detected, by single-crystal XRD, along with other halomethane−chloride interactions. Appropriate density functional theory calculations performed by two complementary methodologies, (i) single-point "quasi-solid state" calculations with topological analysis of the electron density distribution within the framework of Bader theory (QTAIM method) and (ii) Kohn−Sham calculations with periodic boundary conditions, confirmed the existence of the bifurcated interactions and their noncovalent nature. Estimated energies of these interactions vary from 1.1 to 4.7 kcal/mol. Article pubs.acs.org/crystal

Owing to the unknown correlation of a metal’s ligand and its resulting preferred speciation in terms of oxidation state, geometry, and nuclearity, a rational design of multinuclear catalysts remains challenging. With the goal to accelerate the identification of suitable ligands that form trialkylphosphine-derived dihalogen-bridged Ni(I) dimers, we herein employed an assumption-based machine learning approach. The workflow offers guidance in ligand space for a desired speciation without (or only minimal) prior experimental data points. We experimentally verified the predictions and synthesized numerous novel Ni(I) dimers as well as explored their potential in catalysis. We demonstrate C–I selective arylations of polyhalogenated arenes bearing competing C–Br and C–Cl sites in under 5 min at room temperature using 0.2 mol % of the newly developed dimer, [Ni(I)(μ-Br)­PAd2(n-Bu)]2, which is so far unmet with alternative dinuclear or mononuclear Ni or Pd catalysts.

While vinyl cyclopropanes are valuable functional groups in drugs or natural products as well as established precursors to trigger a rich variety of synthetic transformations, their reactive nature can make their installation via direct catalytic approaches challenging. We herein present a modular access to (di)vinyl cyclopropanes under very mild conditions and full conservation of stereochemistry, allowing access to the cis or trans cyclopropane-as well as E or Z vinylstereochemical relationships. Our protocol relies on airstable dinuclear Pd I catalysis, which enables rapid (< 30 min) and selective access to a diverse range of vinyl cyclopropane motifs at room temperature, even on gram scale.

Novel three-component “two saccharins-one dialkylcyanamide” integration.