The treatment of disilenide Tip₂SiSi(Tip)Li (1, Tip = 2,4,6-ⁱPr₃C₆H₂) with P-chloro phosphines affords the phosphino disilenes (2a-d; a: R = Ph, b: R = ⁱPr, c: R = Cy, d: R = ^tBu), which were characterised by multinuclear NMR spectroscopy for 2a-d and a single crystal X-ray diffraction study in case of 2c. As an alternate synthetic method, the diphenyl derivative 2a could also be prepared by reaction of LiPPh₂ with the thermally unstable iododisilene, Tip₂SiSi(Tip)I (3), which in turn was obtained by oxidation of 1 with stoichiometric amounts of iodine. Providing the first example for a SiSi bond with an iodo functionality, disilene 3 was fully characterised by multinuclear NMR and X-ray diffraction. The thermal rearrangement of phosphine disilene 2avia a C–H insertion reaction yields the diastereomeric mixture of a 1-phospha-2,3-disilaindane 4. The structure of the cis-diastereomer of 4 was determined by X-ray diffraction. Finally, the synthesis of first transition metal complex of 2a and 2b by their coordination to the [Pd(PCy₃)] fragment is reported. The solid state structure of complex 5a reveals η²-coordination of the SiSi bond of the phosphino disilene 2a with an intermediate bonding mode between π-complex and metallacyclopropane rather than coordination of the phosphino group.