The crystal structure of the title compound, trans-[PtCl₂(C₁₆H₂₃P)₂], has been determined at 100 K. The Pt atom is located on a twofold axis and adopts a distorted square-planar coordination geometry. The structure is only the second example of a coordination complex containing a derivative of the 4,8-dimethyl-2-phosphabicyclo­[3.3.1]nona­ne (Lim) phosphine ligand family. The ligand contains four chiral C atoms, with the stereochemistry at three of these fixed during synthesis, therefore resulting in two possible ligand stereoisomers. The compound crystallizes in the chiral space group P4₃2₁2 but is racemic, comprising an equimolar mixture of both stereoisomers disordered on a single ligand site. The effective cone angles for both isomers are the same at 146°.

The title compound, trans-[PdCl₂(C₁₆H₁₃PS)₂], forms a monomeric complex with a trans-square-planar geometry. The Pd—P bond lengths are 2.3387 (11) Å, as the Pd atom lies on an inversion point, while the Pd—Cl bond lengths are 2.2950 (12) Å.

The title compound, C₃₀H₂₁O₃P, has a distorted trigonal–pyramidal geometry around the P atom. The P—O bond lengths are between 1.609 (1) and 1.643 (1) Å, and O—P—O bond angles vary between 94.73 (5) and 101.91 (6)°. The crystal structure is stablized by weak π—π and C—Hπ inter­actions.

The title compound, [RhCl(C₁₉H₁₇P)₂(CO)], can be characterized as a Vaska-type complex containing a diphen­yl(4-tol­yl)phosphine ligand. The rhodium(I) metal centre has a square-planar coordination. The molecule is disordered, with the Rh atom lying on an inversion centre. The most important bond lengths and angles include Rh—P = 2.3315 (9) Å, Rh—Cl(trans CO) = 2.405 (2) Å, Rh—C(carbon­yl) = 1.724 (11) Å and Rh—C—O = 178.0 (6)°.

In the title compound, [PdBr₂(C₁₈H₁₅As)₂], the Pd^II ion resides on a centre of symmetry and is coordinated by two As atoms [Pd—As = 2.4184 (3) Å] and two Br anions [Pd—Br = 2.4196 (3) Å] in a slightly distorted square-planar geometry [As—Pd—Br = 90.12 (1)°]. The crystal packing exhibits weak inter­molecular C—HBr inter­actions.

In the title compound, [PdBr₂(C₂₁H₂₁As)₂], the Pd^II ion, residing on a centre of symmetry, is coordinated by two As donor atoms [Pd—As = 2.4276 (2) Å] and two Br anions [Pd—Br = 2.4194 (2) Å] in a distorted square-planar geometry [Br—Pd—As = 87.786 (7)°]. A weak intra­molecular C—HBr inter­action occurs. In the crystal structure, inter­molecular C—HBr inter­actions are observed.

In the title compound, [PdBr₂(C₁₈H₁₂Cl₃P)₂], the Pd^II ion is situated on a centre of symmetry and is coordinated by two Br anions [Pd-Br = 2.4252 (2) Å] and two P-donor ligands [Pd-P = 2.3317 (6) Å] in a slightly distorted square-planar geometry [P-Pd-Br = 86.589 (15)°].

In the title compound, [PdBr₂(C₁₉H₁₇P)₂], the Pd^II ion resides on a centre of symmetry and is coordinated by two Br anions [Pd—Br = 2.4266 (2) Å] and two P-donor ligands [Pd—P = 2.3462 (5) Å] in a slightly distorted square-planar geometry [P—Pd—Br = 93.528 (12)°]. Weak inter­molecular C—HBr hydrogen bonds link mol­ecules into chains extended in [10].

The title compound, [RhCl(C₂₂H₃₄OP)₂(CO)], can be described as one of a few Rh^I Vaska-type complexes containing a (2-naphth­yloxy)diphenyl­phosphine ligand and has a square-planar geometry about the rhodium(I) metal centre, which lies on an inversion centre, so that the carbonyl and chloro ligands are disordered. The most important bond lengths and angle include Rh—P = 2.305 (1) Å, Rh—Cl = (trans CO) = 2.374 (2) Å, Rh—C (carbon­yl) = 1.818 (6) Å and Rh—C—O = 178.1 (10)°. A weak π–π inter­molecular stacking is observed, with an inter­planar distance of 3.377 (2) Å.

The title compound, [Ag(AsC₁₈H₁₅)₄]PF₆, crystallizes with the cation on a threefold rotation axis and the anions on positions with site symmetry . The Ag atom is surrounded by four arsine ligands forming a distorted tetra­hedral configuration. The Ag—As distances are 2.6381 (6) and 2.6499 (9) Å, and the As—Ag—As angles are 108.91 (1) and 110.03 (1)°.

The title compound, [PtCl₂(C₁₈H₁₂Cl₃P)₂]·C₂H₃N, packs as monomeric units with a square-planar geometry around the Pt^II atom. The two tris­(4-chloro­phen­yl)phosphane ligands are coordinated in a cis orientation, with P—Pt—P and Cl—Pt—Cl angles of 99.36 (2) and 88.02 (2)°, respectively. In the crystal, C—HN inter­actions are observed between the phenyl rings and the acetonitrile solvent mol­ecules.

In the title compound, trans-[RhCl(C₂₀H₁₇P)₂(CO)], the Rh^I atom is situated on a center of symmetry, resulting in a statistical 1:1 disorder of the chloride [Rh—Cl = 2.383 (2) Å] and carbonyl [Rh—C = 1.752 (7) Å] ligands. The distorted trans square-planar environment is completed by two P atoms [Rh—P = 2.3251 (4) Å] from two diphen­yl(4-vinyl­phen­yl)phosphane ligands. The vinyl group is disordered over two sets of sites in a 0.668 (10):0.332 (10) ratio. The crystal packing exhibits weak C—HCl and C—HO hydrogen bonds and π–π inter­actions between the phenyl rings of neighbouring mol­ecules, with a centroid–centroid distance of 3.682 (2) Å.

The title compound, [RhBr(C₁₈H₁₅P)₂(CO)], can be characterized as a rhodium(I) Vaska-type compound based only on the spectroscopic [ν_KBr(CO), ³¹P] data. A low-temperature X-ray crystallographic analysis shows that the compound possesses a crystallographically imposed centre of symmetry with a statistically disordered Br atom and CO group. The essentially different occupancies for the Br atom and the CO group [0.283 (2) and 0.717 (2), respectively] suggest that the compound exists as a mixture of rhodium(0), rhodium(I) and rhodium(II) complexes.

The centrosymmetric title compound, [PdCl₂(C₁₉H₁₇P)₂], crystallizes with a square-planar geometry about the Pd^II metal centre. The most important bond distances include Pd—P (trans P) of 2.3404 (9) Å and Pd—Cl (trans Cl) of 2.2977 (12) Å. Weak intra- and inter­molecular hydrogen bonding is observed in the solid-state structure between the chloro and phenyl H atoms. This weak inter­molecular hydrogen-bonding pattern forms a one-dimensional chain along the b axis.