Phosphorus-Bismuth -Substituted Acenaphthenes: A Synthetic, Structural, and Computational Study.

A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the positions were synthesized and fully characterized, including single-crystal X-ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P-Bi bond. The series includes the phosphine-bismuthine Acenap(PPr)(BiPh) (; Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PPr)(BiPhX) (- and ; X = BF Cl, Br, I, SPh), displaying varying degrees of ionicity.

A Study of Through-Space and Through-Bond J Coupling in a Rigid Nonsymmetrical Bis(phosphine) and Its Metal Complexes.

A series of representative late d-block metal complexes bearing a rigid bis(phosphine) ligand, iPrP-Ace-PPh (L, Ace = acenaphthene-5,6-diyl), was prepared and fully characterized by various techniques, including multinuclear NMR and single-crystal X-ray diffraction. The heteroleptic nature of the peri-substituted ligand L allows for the direct observation of the J couplings in the P{H} NMR spectra. Magnitudes of J are correlated with the identity and geometry of the metal and the distortions of the ligand L.

Geminally Substituted Tris(acenaphthyl) and Bis(acenaphthyl) Arsines, Stibines, and Bismuthine: A Structural and Nuclear Magnetic Resonance Investigation.

Tris(acenaphthyl)- and bis(acenaphthyl)-substituted pnictogens (iPr2P-Ace)3E (2-4) (E = As, Sb, or Bi; Ace = acenaphthene-5,6-diyl) and (iPr2P-Ace)2EPh (5 and 6) (E = As or Sb) were synthesized and fully characterized by multinuclear nuclear magnetic resonance (NMR), high-resolution mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. The molecules adopt propeller-like geometries with the restricted rotational freedom of the sterically encumbered iPr2P-Ace groups resulting in distinct NMR features. In the tris(acenaphthyl) species (2-4), the phosphorus atoms are isochronous in the (31)P{(1)H} NMR spectra, and the rotation of the three acenaphthyl moieties around the E-Cipso bond is locked.

Diphosphane 2,2'-binaphtho[1,8-de][1,3,2]dithiaphosphinine and the easy formation of a stable phosphorus radical cation.

A convenient synthesis route to 2,2'-binaphtho[1,8-de][1,3,2]di-thiaphosphinine () was found. Its stable radical cation 3˙(+) was accessed easily through one-electron oxidation with NOBF4.

Structural diversity of bimetallic rhodium and iridium half sandwich dithiolato complexes.

The synthesis of a range of rhodium(iii) and iridium(iii) half sandwich complexes with aryl dithiolato ligands of varying geometry and flexibility are reported. These include dinuclear [Cp*M(S-R-S)]2 complexes 3b and 4b, M = Rh, Ir; S-R-S = naphthalene-1,8-dithiolate (b) and four dinuclear complexes bearing bridging dithiolate ligands [(Cp*M)2(μ2-Cl)(μ2-S-R-S)]Cl 3c, 4c, 5b, 6b, M = Rh, Ir; S-R-S = naphthalene-1,8-dithiolate (b) or acenaphthene-5,6-dithiolate (c). The introduction of a less rigid biphenyl dithiolate backbone resulted in the tetranuclear dicationic complex [(Cp*Rh)4(S-R-S)3]Cl2 (3d), S-R-S = biphenyl-2,2'-dithiolate (d) with dithiolate ligands in two different bridging modes.