Reaction of ( p -tol 3 P) 2 PtCl 2 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/THF/reflux) gives monosubstituted trans -Cl( p -tol 3 P) 2 Pt(CC) 2 SiMe 3 (63%), which with wet n -Bu 4 N + F − yields trans -Cl( p -tol 3 P) 2 Pt(CC) 2 H ( 2 , 96%). Hay oxidative homocoupling (O 2 /CuCl/TMEDA) gives all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 Cl ( 3 , 68%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/rt) affords monosubstituted all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (46%), which is converted by a similar desilylation/homocoupling sequence to all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 3 Pt(P p -tol 3 ) 2 Cl ( 7 ; 79%). Reaction of ( p -tol 3 P) 2 PtCl 2 and excess H(CC) 2 SiMe 3 (HNEt 2 /cat. CuI) gives trans -Me 3 Si(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (78%), which with wet n -Bu 4 N + F − affords transmore »
En route to diplatinum polyynediyl complexes trans,trans-(Ar)(R3P)2Pt(C≡C)nPt(PR3)2(Ar): Untold tales, including end-group strategies
Reactions of {(C 6 F 5 )Pt[S(CH 2 CH 2 -) 2 ](μ-Cl)} 2 and R 3 P yield the bis(phosphine) species trans -(C 6 F 5 )(R 3 P) 2 PtCl [R = Et ( Pt'Cl ), Ph, ( p -CF 3 C 6 H 4 ) 3 P; 88-81 %]. Additions of Pt'Cl and H(C≡C) n H ( n = 1, 2; HNEt 2 , 20 mol % CuI) give Pt'C 2 H (37 %, plus Pt'I , 16 %) and Pt'C 4 H (88 %). Homocoupling of Pt'C 4 H under Hay conditions (O 2 , CuCl, TMEDA, acetone) gives Pt'C 8 Pt' (85 %), but Pt'C 2 H affords only traces of Pt'C 4 Pt' . However, condensation of Pt'C 4 H and Pt'Cl (HNEt 2 , 20 mol % CuI) yields Pt'C 4 Pt' (97 %). Hay heterocouplings of Pt'C 4 H or trans -( p -tol)(Ph 3 P) 2 Pt(C≡C) 2 H ( Pt*C 4 H ) and excess HC≡CSiEt 3 give Pt'C 6 SiEt 3 (76 %) or Pt*C 6 SiEt 3 (89 %). The latter and wet n -Bu 4 N + F - react to yield labile Pt*C 6 H (60 more »
- Publication Date:
- NSF-PAR ID:
- 10163957
- Journal Name:
- Pure and Applied Chemistry
- Volume:
- 80
- Issue:
- 3
- Page Range or eLocation-ID:
- 459 to 474
- ISSN:
- 0033-4545
- Sponsoring Org:
- National Science Foundation
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