Electron‐Transfer Studies of trans‐Platinum Bis(acetylide) Complexes. Issue 32 (30th September 2014)

• Record Type: Journal Article
• Authors: Miesel, Dominique; Hildebrandt, Alexander; Rüffer, Tobias; Schaarschmidt, Dieter; Lang, Heinrich
• Is Part Of: European journal of inorganic chemistry. Issue 32(2014)
• Page Start: 5541
• Page End: 5553
• Publication Date: 2014-09-30
• Subjects: Platinum -- Phosphanes -- Structure elucidation -- Electrochemistry -- Electron transfer; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201402686
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The complexes trans ‐[Pt(C≡CFc)2 (PFc m n Bu3– m )2 ] (Fc = ferrocenyl; m = 0, 9a ; m = 1, 9b ; m = 2, 9c ) were prepared by the reactions of PFc m n Bu3– m ( m = 0, 3a ; m = 1, 3b ; m = 2, 3c ) with cis ‐[PtCl2 (SEt2 )2 ] (6 ) to form [PtCl2 (PFc m n Bu3– m )2 ] ( m = 0, 7a ; m = 1, 7b ; m = 2, 7c ), which on treatment with [CuC≡CFc] (8 ) produced9a –9c . The reactions of PFc m n Bu3– m ( m = 1–3; m = 3, 3d ) with S8 or Se gave (S=)PFc m n Bu3– m ( m = 1, 4b ; m = 2, 4c ; m = 3, 4d ) and (Se=)PFc m n Bu3– m ( m = 1, 5b ; m = 2, 5c ; m = 3, 5d ). Compounds5d, 7b, 7c, 9b, and9c were structurally characterized by single‐crystal X‐ray diffraction studies; a trans arrangement of the phosphine units at the Pt center is typical. The redox behavior of3, 4, 7, and9 was investigated by cyclic and square‐wave voltammetry. The Fc units of9a –9c could be oxidized separately indicating electronic interactions between the Fc/Fc + groups of the FcC≡C units [Δ E°′ = 105 (9a ), 115 (9b ), 120 mV (9c )]. Cationic [9b ] + and [9c ] + exhibit weak intervalence charge‐transfer (IVCT) absorptions at$\tilde {\nu}$ = 6700 cm –1 . Abstract : The synthesis of trans ‐[Pt(C≡CFc)2 (PFc m n Bu3– m )2 ] ( m = 0, 1, 2; Fc = ferrocenyl) is presented. Spectroelectrochemical investigations indicate electronic communication between the iron centers of the FcC≡C units; therefore, these compounds are classified as weakly coupled class II systems, according to Robin and Day.