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Reaction of ( p -tol 3 P) 2 PtCl 2 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/THF/reflux) gives monosubstituted trans -Cl( p -tol 3 P) 2 Pt(CC) 2 SiMe 3 (63%), which with wet n -Bu 4 N + F − yields trans -Cl( p -tol 3 P) 2 Pt(CC) 2 H ( 2 , 96%). Hay oxidative homocoupling (O 2 /CuCl/TMEDA) gives all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 Cl ( 3 , 68%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/rt) affords monosubstituted all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (46%), which is converted by a similar desilylation/homocoupling sequence to all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 3 Pt(P p -tol 3 ) 2 Cl ( 7 ; 79%). Reaction of ( p -tol 3 P) 2 PtCl 2 and excess H(CC) 2 SiMe 3 (HNEt 2 /cat. CuI) gives trans -Me 3 Si(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (78%), which with wet n -Bu 4 N + F − affords trans -H(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Hay oxidative cross coupling with 2 (1 : 4) gives all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 2 Pt(P p -tol 3 ) 2 Cl ( 10 , 36%) along with homocoupling product 3 (33%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 2/rt) yields all- trans -Me 3 Si(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 ( 17 , 77%), which with wet n -Bu 4 N + F − gives all- trans -H(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Reaction of 3 and excess Me 3 P gives all- trans -Cl(Me 3 P) 2 Pt(CC) 4 Pt(PMe 3 ) 2 Cl ( 4 , 86%). A model reaction of trans -( p -tol)( p -tol 3 P) 2 PtCl and KSAc yields trans -( p -tol)( p -tol 3 P) 2 PtSAc ( 12 , 75%). Similar reactions of 3 , 7 , 10 , and 4 give all- trans -AcS[(R 3 P) 2 Pt(CC) 4 ] n Pt(PR 3 ) 2 SAc (76–91%). The crystal structures of 3 , 17 , and 12 are determined. The first exhibits a chlorine–chlorine distance of 17.42 Å; those in 10 and 7 are estimated as 30.3 Å and 43.1 Å.