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A Caged Neutral 17-Valence-Electron Iron(I) Radical [Fe(CO)(Cl)(P((CH))P)]: Synthetic, Structural, Spectroscopic, Redox, and Computational Studies.
Inorg Chem
September 2024
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, United States.
UV irradiation of yellow CHCl solutions of -Fe(CO)(P((CH))P) () and PMe (10 equiv) gives, in addition to the previously reported dibridgehead diphosphine P((CH))P (46%), a green paramagnetic complex that crystallography shows to be the trigonal-bipyramidal iron(I) radical -[Fe(CO)(Cl)(P((CH))P)] (; 31% after workup). This is a rare example of an isolable species of the formula [Fe(CO)(L)(X)] ( = 0-3, L = two-electron-donor ligand; X = one-electron-donor ligand). Analogous precursors with longer P(CH)P segments ( = 12, 14, 16, 18) give only the demetalated diphosphines, and a rationale is proposed.
View Article and Find Full Text PDFMolecules that Turn Themselves Inside-Out: Tuning in/out Equilibria and Homeomorphic Isomerization in Macrobicyclic Dibridgehead Diphosphines P((CH ) ) P Newly Accessible by Earth-Abundant-Metal Templates.
Chemistry
December 2023
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA.
Article Synopsis
- The photolysis of trans-Fe(CO)(P((CH)n)P) compounds offers a new, efficient method to produce macrobicyclic dibridgehead diphosphines, leading to the discovery of isomer mixtures that can interconvert at higher temperatures.
- Variable-temperature phosphorus NMR spectroscopy is used to study and categorize kinetic behaviors, activation parameters, and isomerization processes, providing a comprehensive insight into the transformations among different isomers within a homologous series of aliphatic bicyclic compounds.
- Structural analysis of isomeric diborane adducts is performed, with crystal structures confirming isomer identities and revealing unique conformations of the compounds,
The diphosphine complexes - or -[upper bond 1 start]PtCl(P((CH) )P[upper bond 1 end]) ( = b/12, c/14, d/16, e/18) are demetalated by MC[triple bond, length as m-dash]X nucleophiles to give the title compounds (P((CH) ))P (3b-e, 91-71%). These "empty cages" react with PdCl or PtCl sources to afford -[upper bond 1 start]MCl(P((CH) )P[upper bond 1 end]). Low temperature P NMR spectra of 3b and c show two rapidly equilibrating species (3b, 86 : 14; 3c, 97 : 3), assigned based upon computational data to , (major) and , isomers.
View Article and Find Full Text PDFSquare-Planar and Octahedral Gyroscope-Like Metal Complexes Consisting of Dipolar Rotators Encased in Dibridgehead Di(triaryl)phosphine Stators: Syntheses, Structures, Dynamic Properties, and Reactivity.
Inorg Chem
October 2022
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, United States.
For a variety of purposes, it is of interest to embed metals in cagelike -spanning di(triaryl)phosphine ligands. Toward this end, a combination of P(-CHO(CH)CH═CH) [; = 4 (), 5 (), 6 (), and 7 ()], [Rh(COD)(μ-Cl)], and CO gives square-planar -Rh(CO)(Cl)[P(-CHO(CH)CH═CH)] (-). Reactions of - with Grubbs' catalyst (first generation) and then H (catalyst PtO) yield the title compounds -Rh(CO)(Cl)[P(-CHO(CH)O--CH)P] ( = 2 + 2, -; 26-41% from -).
View Article and Find Full Text PDFPlatinum(II) alkyl complexes of chelating dibridgehead diphosphines P((CH))P ( = 14, 18, 22); facile / isomerizations interconverting gyroscope and parachute like adducts.
Dalton Trans
September 2021
Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842-3012, USA.
The gyroscope like dichloride complexes -Pt(Cl)(P((CH))P) (-2; = c, 14; e, 18; g, 22) and MeLi (2 equiv.) react to yield the parachute like dimethyl complexes -Pt(Me)(P((CH))P) (-4c,e,g, 70-91%). HCl (1 equiv.
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