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1. POCOP-type cobalt and nickel pincer complexes bearing an appended phosphinite group

   https://doi.org/10.1139/cjc-2020-0137  

   Li, Yingze ; Krause, Jeanette A. ; Guan, Hairong ( April 2021 , Canadian Journal of Chemistry)

   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. 

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2. Crystal structures of phosphine-supported (η 5 -cyclopentadienyl)molybdenum(II) propionyl complexes

   https://doi.org/10.1107/S2056989021008008  

   Whited, Matthew T. ; Ball, Margaret A. ; Block, Alison ; Brewster, Benjamin A. ; Ferrer, LouLou ; Jin-Lee, Helen J. ; King, Colby J. ; North, Jamie D. ; Shelton, Inger L. ; Wilson, David G. ( September 2021 , Acta Crystallographica Section E Crystallographic Communications)

   Three cyclopentadienylmolybdenum(II) propionyl complexes featuring triarylphosphine ligands with different para substituents, namely, dicarbonyl(η 5 -cyclopentadienyl)propionyl(triphenylphosphane-κ P )molybdenum(II), [Mo(C 5 H 5 )(C 3 H 5 O)(C 18 H 15 P)(CO) 2 ], ( 1 ), dicarbonyl(η 5 -cyclopentadienyl)propionyl[tris(4-fluorophenyl)phosphane-κ P ]molybdenum(II), [Mo(C 5 H 5 )(C 3 H 5 O)(C 18 H 12 F 3 P)(CO) 2 ], ( 2 ), and dicarbonyl(η 5 -cyclopentadienyl)propionyl[tris(4-methoxyphenyl)phosphane-κ P ]molybdenum(II) dichloromethane solvate, [Mo(C 5 H 5 )(C 3 H 5 O)(C 21 H 21 O 3 P)(CO) 2 ]·CH 2 Cl 2 , ( 3 ), have been prepared from the corresponding ethyl complexes via phosphine-induced migratory insertion. These complexes exhibit four-legged piano-stool geometries with molecular structures quite similar to each other and to related acetyl complexes. The extended structures of the three complexes differ somewhat, with the para substituent of the triarylphosphine of ( 2 ) (fluoro) or ( 3 ) (methoxy) engaging in non-classical C—H...F or C—H...O hydrogen-bonding interactions. The structure of ( 3 ) exhibits modest disorder in the position of one Cl atom of the dichloromethane solvent, which was modeled with two sites showing approximately equivalent occupancies [0.532 (15) and 0.478 (15)]. 

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3. Addition of H 2 Across a Cobalt–Phosphorus Bond

   https://doi.org/10.1002/anie.201710100  

   Poitras, Andrew M. ; Knight, Sadie E. ; Bezpalko, Mark W. ; Foxman, Bruce M. ; Thomas, Christine M. ( January 2018 , Angewandte Chemie International Edition)

   Addition of H₂across the cobalt–phosphorus bond of (PPP)CoPMe₃(3) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N‐heterocyclic phosphido (NHP⁻) donor. The chlorophosphine Co^IIcomplex (PP^ClP)CoCl₂(2) can be generated through coordination of the chlorophosphine ligand (PP^ClP,1) to CoCl₂. Subsequent reduction of2with KC₈in the presence of PMe₃generates (PPP)CoPMe₃(3), in which both the phosphorus and cobalt centers have been reduced. The addition of 1 atm of H₂to complex3cleanly affords (PP^HP)Co(H)PMe₃(4), in which H₂has ultimately been added across the metal–phosphorus bond. Complex4was characterized spectroscopically and using computational methods to predict its geometry.

    

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4. Addition of H 2 Across a Cobalt–Phosphorus Bond

   https://doi.org/10.1002/ange.201710100  

   Poitras, Andrew M. ; Knight, Sadie E. ; Bezpalko, Mark W. ; Foxman, Bruce M. ; Thomas, Christine M. ( January 2018 , Angewandte Chemie)

   Addition of H₂across the cobalt–phosphorus bond of (PPP)CoPMe₃(3) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N‐heterocyclic phosphido (NHP⁻) donor. The chlorophosphine Co^IIcomplex (PP^ClP)CoCl₂(2) can be generated through coordination of the chlorophosphine ligand (PP^ClP,1) to CoCl₂. Subsequent reduction of2with KC₈in the presence of PMe₃generates (PPP)CoPMe₃(3), in which both the phosphorus and cobalt centers have been reduced. The addition of 1 atm of H₂to complex3cleanly affords (PP^HP)Co(H)PMe₃(4), in which H₂has ultimately been added across the metal–phosphorus bond. Complex4was characterized spectroscopically and using computational methods to predict its geometry.

    

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5. Structural diversity in copper(I) iodide complexes with 6-thioxopiperidin-2-one, piperidine-2,6-dithione and isoindoline-1,3-dithione ligands

   https://doi.org/10.1107/S2056989020009676  

   Wheaton, Amelia M. ; Guzei, Ilia A. ; Berry, John F. ( August 2020 , Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   Copper(I) iodide complexes are well known for displaying a diverse array of structural features even when only small changes in ligand design are made. This structural diversity is well displayed by five copper(I) iodide compounds reported here with closely related piperidine-2,6-dithione (SNS), isoindoline-1,3-dithione (SNS6), and 6-thioxopiperidin-2-one (SNO) ligands: di-μ-iodido-bis[(acetonitrile-κ N )(6-sulfanylidenepiperidin-2-one-κ S )copper(I)], [Cu 2 I 2 (CH 3 CN) 2 (C 5 H 7 NOS) 2 ] ( I ), bis(acetonitrile-κ N )tetra-μ 3 -iodido-bis(6-sulfanylidenepiperidin-2-one-κ S )- tetrahedro -tetracopper(I), [Cu 4 I 4 (CH 3 CN) 4 (C 5 H 7 NOS) 4 ] ( II ), catena -poly[[(μ-6-sulfanylidenepiperidin-2-one-κ 2 O : S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NOS)] n ( III ), poly[[(piperidine-2,6-dithione-κ S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NS 2 )] n ( IV ), and poly[[(μ-isoindoline-1,3-dithione-κ 2 S : S )copper(I)]-μ 3 -iodido], [CuI(C 8 H 5 NS 2 )] n ( V ). Compounds I and II crystallize as discrete dimeric and tetrameric complexes, whereas III , IV , and V crystallize as polymeric two-dimensional sheets. To the best of our knowledge, compound III is the first instance of an extended hexagonal [Cu 3 I 3 ] structure that is not supported by bridging ligands. Structures I , II , and IV display weak to moderately strong Cu...Cu cuprophilic interactions [Cu...Cu internuclear distances range between 2.5803 (10) and 2.8485 (14) Å]. All structures except III display weak hydrogen-bonding interactions between the N—H of the ligand and the μ 2 and μ 3 -I − atoms. Structure III contains classical N–H...O interactions between the SNO ligands that connect the molecules in a three-dimensional framework. Complex V features π–π stacking interactions between the aryl rings of the SNS6 ligands within the same polymeric sheet. In structure IV , there were three partially occupied solvent molecules of dichloromethane and one partially occupied molecule of acetonitrile present in the asymmetric unit. The SQUEEZE routine [Spek (2015). Acta Cryst . C 71 , 9–18] was used to correct the diffraction data for diffuse scattering effects and to identify the solvent molecules. The given chemical formula and other crystal data do not take into account the solvent molecules. 

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