The reaction of SiX4 (X = Cl or Br) with PMe3 in anhydrous CH2Cl2 forms trans-[SiX4(PMe3)(2)], while the cliphosphines, Me2P(CH2)(2)PMe2, Et2P(CH2)(2)PEt2, and o-C6H4(PMe2)(2) form cis-[SiX4(diphosphine)], all containing six coordinate silicon centers. With Me2PCH2PMe2 the product was trans-[SiCl4(k(1)-Me2PCH2PMe2)(2)]. The complexes have been characterized by X-ray crystallography, microanalysis, IR, and multinuclear (H-1, C-13{H-1}, and P-31-{H-1}) NMR spectroscopies. The complexes are stable solids and not significantly dissociated in nondonor solvents, although they are very moisture and oxygen sensitive. This stability conflicts with the predictions of recent density functional theory (DFT) calculations (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) which suggested six-coordinate silicon phosphines would be unstable, and also contrasts with the failure to isolate complexes with SiF4 (George et al. Dalton Trans. 2011, 40, 1584-1593). No reaction occurred between phosphines and SiI4 or with SiX4 and arsine ligands including AsMe3 and o-C6H4(AsMe2)(2). Attempts to make five-coordinate [SiX4(PR3)] using the sterically bulky phosphines, (PBu3)-Bu-t, (PPr3)-Pr-i, or PCy3 failed, with no apparent reaction occurring, consistent with predictions (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) that such compounds would be very endothermic, while the large cone angles of the phosphines presumably preclude formation of six coordination at the small silicon center. The reaction of Si2Cl6 with PMe3 or the diphosphines in CH2Cl2 results in instant disproportionation to the SiCl4 adducts and polychlorosilanes, but from hexane solution very unstable white {Si2Cl6(PMe3)(2)] and [Si2Cl6(diphosphine)] (diphosphine = Me2P(CH2)(2)PMe2 or o-C6H4(PMe2)(2)) precipitate. The reactions of SiHCl3 with PMe3 and Me2P(CH2)(2)PMe2 also produce the SiCl4 adducts, but using Et2P(CH2)(2)PEt2, colorless [SiHCl3{Et2P(CH2)(2)PEt2}] was isolated, which was characterized by an X-ray structure which showed a pseudo octahedral complex with the Si-H trans to P. Attempts to reduce the silicon(IV) phosphine complexes to silicon(II) were unsuccessful, contrasting with the isolation of stable N-heterocyclic carbene adducts of Si(II).