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1. Copper Selenophosphate, Cu ₃ PSe ₄ , Nanoparticle Synthesis: Octadecane Is the Key to a Simplified, Atom-Economical Reaction

   https://doi.org/10.1021/acs.nanolett.3c02620  

   Neisius, Nathan A; MacHale, Luke T; Snyder, Erin R; Finke, Richard G; Prieto, Amy L (December 2023, Nano Letters)

   Nanoparticle syntheses are designed to produce thedesired product in high yield but traditionally neglect atom economy. Here we report that the simple, but significant, change of the solvent from 1-octadecene (1-ODE) to the operationally inert octadecane (ODA) permits an atom-economical synthesis of copper selenophosphate (Cu3PSe4) nanoparticles. This change eliminates the competing selenium (Se) delivery pathways from our first report that required an excess of Se. Instead Se0 powder is dispersed in ODA, which promotes a formal eight-electron transfer between Cu3−xP and Se0. Powder X-ray diffraction and transmission electron microscopy confirm the purity of the Cu3PSe4, while 1H and 13C NMR indicate the absence of oxidized ODA or Se species. We utilize the direct pathway to gain insights into stoichiometry and ligand identity using thermogravimetric analysis and X-ray photoelectron spectroscopy. Given the prevalence of 1- ODE in nanoparticle synthesis, this approach could be applied to other chalcogenide reaction pathways to improve stoichiometry and atom-economy. 

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2. Solid-state ¹¹ B NMR studies of coinage metal complexes containing a phosphine substituted diboraanthracene ligand

   https://doi.org/10.1039/d1dt02981a  

   Huynh, Winn; Taylor, Jordan W.; Harman, W. Hill; Conley, Matthew P. (October 2021, Dalton Transactions)

   Transition metal interactions with Lewis acids (M → Z linkages) are fundamentally interesting and practically important. The most common Z-type ligands contain boron, which contains an NMR active 11 B nucleus. We measured solid-state 11 B{ 1 H} NMR spectra of copper, silver, and gold complexes containing a phosphine substituted 9,10-diboraanthracene ligand (B 2 P 2 ) that contain planar boron centers and weak M → BR 3 linkages ([(B 2 P 2 )M][BAr F 4 ] (M = Cu (1), Ag (2), Au (3)) characterized by large quadrupolar coupling ( C Q ) values (4.4–4.7 MHz) and large span ( Ω ) values (93–139 ppm). However, the solid-state 11 B{ 1 H} NMR spectrum of K[Au(B 2 P 2 )] − (4), which contains tetrahedral borons, is narrow and characterized by small C Q and Ω values. DFT analysis of 1–4 shows that C Q and Ω are expected to be large for planar boron environments and small for tetrahedral boron, and that the presence of a M → BR 3 linkage relates to the reduction in C Q and 11 B NMR shielding properties. Thus solid-state 11 B NMR spectroscopy contains valuable information about M → BR 3 linkages in complexes containing the B 2 P 2 ligand. 

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3. Synthesis of diphenyl-(2-thienyl)phosphine, its chalcogenide derivatives and a series of novel complexes of lanthanide nitrates and triflates

   https://doi.org/10.1039/d2dt01570f  

   Luster, Troy; Van de Roovaart, Hannah J.; Korman, Kyle J.; Sands, Georgia G.; Dunn, Kylie M.; Spyker, Anthony; Staples, Richard J.; Biros, Shannon M.; Bender, John E. (June 2022, Dalton Transactions)

   A novel synthesis of diphenyl(2-thienyl)phosphine, along with its’ oxide, sulfide and selenide derivatives, is reported here. These phosphines have been characterized by NMR, IR, MS and X-Ray crystallography. The phosphine oxide derivative was reacted with a selection of lanthanide( iii ) nitrates and triflates, LnX 3 , to give the resultant metal–ligand complexes. These complexes have also been characterized by NMR, IR, MS and X-Ray crystallography. Single crystal X-Ray diffraction data shows a difference in metal–ligand complex stoichiometry and stereochemistry depending on the counteranion (nitrate vs. triflate). The [Ln(Ar 3 PO) 3 (NO 3 ) 3 ] ligand–nitrate complexes are nine-coordinate to the metal in the solid state (bidentate nitrate), featuring a 1 : 3 lanthanide–ligand ratio and bear an overall octahedral arrangement of the six, coordinated ligands. Our [Ln(Ar 3 PO) 3 (NO 3 ) 3 ] ligand–nitrate complexes gave three examples of fac -stereochemistry, where mer -stereochemistry is almost universally observed in the literature of highly related [Ln(Ar 3 PO) 3 (NO 3 ) 3 ] complexes. For the Tb complexes, two different arrangements of the ligands around the metal were observed in the solid state for [Tb(Ar 3 PO) 3 (NO 3 ) 3 ] and [Tb(Ar 3 PO) 4 (OTf) 2 ] [OTf]. [Tb(Ar 3 PO) 3 (NO 3 ) 3 ] is strictly nine-coordinate, ligand mer -stereochemistry in the solid state, and [Tb(Ar 3 PO) 4 (OTf) 2 ] [OTf] is strictly octahedral, six-coordinate, with a square-planar stereochemical arrangement of the phosphine oxide ligands around the metal. 

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4. 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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5. Distinct modes of Si–H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand

   https://doi.org/10.1039/D2DT02175G  

   Talosig, Rain A; Cosio, Mario N.; Morse, Benjamin; Nguyen, Vinh T.; Kosanovich, Alex J.; Pell, Christopher J.; Li, Chun; Bhuvanesh, Nattamai; Zhou, Jia; Larsen, Anna S.; et al (September 2022, Dalton Transactions)

   Syntheses of Rh complexes of the phosphine-amido-silane SiNP ligand are reported. The reaction of the parent (SiNP)H ligand (4) with 0.5 equiv. [(COE)RhCl] 2 (COE = cis -cyclooctene) in the presence of NaN(SiME 3 ) 2 resulted in the formation of (SiNP)Rh(COE) (5). Compound 5 was converted to a series of (SiNP)Rh(P(OR) 3 ) complexes 6–10 (R = Ph, i Pr, n Bu, Et, or Me) by treatment with the corresponding phosphite. NMR and XRD structural data, as well as the DFT computational analysis indicate that compounds 5–10 are divided into two structural Types ( A and B ), differing in the nature of the interaction of the Si–H bond of the SiNP ligand with Rh. 

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