Wire like diplatinum, triplatinum, and tetraplatinum complexes featuring X[PtC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]C]mPtX segments; iterative syntheses and functionalization for measurements of single molecule properties. Academic Article uri icon

abstract

  • Reaction of (p-tol3P)2PtCl2 and Me3Sn(C[triple bond, length as m-dash]C)2SiMe3 (1:1/THF/reflux) gives monosubstituted trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)2SiMe3 (63%), which with wet n-Bu4N+ F- yields trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)2H (2, 96%). Hay oxidative homocoupling (O2/CuCl/TMEDA) gives all-trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2Cl (3, 68%). Reaction of 3 and Me3Sn(C[triple bond, length as m-dash]C)2SiMe3 (1:1/rt) affords monosubstituted all-trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2SiMe3 (46%), which is converted by a similar desilylation/homocoupling sequence to all-trans-Cl[(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4]3Pt(Pp-tol3)2Cl (7; 79%). Reaction of (p-tol3P)2PtCl2 and excess H(C[triple bond, length as m-dash]C)2SiMe3 (HNEt2/cat. CuI) gives trans-Me3Si(C[triple bond, length as m-dash]C)2Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2SiMe3 (78%), which with wet n-Bu4N+ F- affords trans-H(C[triple bond, length as m-dash]C)2Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2H (96%). Hay oxidative cross coupling with 2 (1:4) gives all-trans-Cl[(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4]2Pt(Pp-tol3)2Cl (10, 36%) along with homocoupling product 3 (33%). Reaction of 3 and Me3Sn(C[triple bond, length as m-dash]C)2SiMe3 (1:2/rt) yields all-trans-Me3Si(C[triple bond, length as m-dash]C)2(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2SiMe3 (17, 77%), which with wet n-Bu4N+ F- gives all-trans-H(C[triple bond, length as m-dash]C)2(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2H (96%). Reaction of 3 and excess Me3P gives all-trans-Cl(Me3P)2Pt(C[triple bond, length as m-dash]C)4Pt(PMe3)2Cl (4, 86%). A model reaction of trans-(p-tol)(p-tol3P)2PtCl and KSAc yields trans-(p-tol)(p-tol3P)2PtSAc (12, 75%). Similar reactions of 3, 7, 10, and 4 give all-trans-AcS[(R3P)2Pt(C[triple bond, length as m-dash]C)4]nPt(PR3)2SAc (76-91%). The crystal structures of 3, 17, and 12 are determined. The first exhibits a chlorine-chlorine distance of 17.42 ; those in 10 and 7 are estimated as 30.3 and 43.1 .

published proceedings

  • Dalton Trans

altmetric score

  • 1

author list (cited authors)

  • Zheng, Q., Schneider, J. F., Amini, H., Hampel, F., & Gladysz, J. A.

citation count

  • 10

complete list of authors

  • Zheng, Qinglin||Schneider, Jakob F||Amini, Hashem||Hampel, Frank||Gladysz, John A

publication date

  • April 2019