462121-60-4Relevant academic research and scientific papers
Synthesis of Pt(II)-Pt(II) and Pt/Pd(II)-Pt(0) monoalkynylphosphine bridging complexes
Forniés, Juan,García, Ana,Gómez, Julio,Lalinde, Elena,Moreno, M. Teresa
, p. 3733 - 3743 (2002)
The monoalkynylphosphine complexes cis-[Pt(C6F5)2(PPh2C≡CR)(tht)] (R = Ph 1a, Tol 1b, tBu 1e, tht = tetrahydrothiophene) have been prepared by bridge splitting [{Pt(C6F5)2(μ-tht)}2] or by displacement of only one tht ligand from cis- [Pt(C6F5)2(tht)2] with PPh2C≡CR. Complexes 1 react with cis- [Pt(C6F5)2(thf)2] to give binuclear derivatives [(C6F5)2Pt(μ-tht)-(μ-1κP:2η 2-PPh2C≡CR)Pt(C6F5)2 ] (R = Ph 2a, Tol 2b, tBu 2c), containing a mixed tht/PPh2C= CR bridging system. In contrast, treatment of 1 with [Pt(η2-C2H4)(PPh3)2] affords mixed-valence Pt(II)-Pt(0) complexes [{(C6F5)2(tht)Pt(μ-1κP:2η2 -PPh2C≡CR)}Pt(PPh3)2] (R = Ph 3a, Tol 3b) stabilized by only one κP:η2 bridging alkynyl phosphine. The molecular structures of 2a and 3a have been confirmed by single-crystal X-ray diffraction. Similarly, reactions of cis-bis(diphenylphosphino)alkyne complexes cis- [M(C6F5)2(PPh2C≡CR)2 ] and cis-[Pt(C≡CR′)2-(PPh2C≡CR)2] (M = Pt, Pd; R = Ph, Tol; R′ = Ph, tBu) with 1 or 2 equiv of [Pt(η2-C2H4)-(PPh3)2] yield the corresponding mixed-valence binuclear complexes cis-[{(C6F5)2M(PPh2C≡ CR)(μ-1-κP:2η2-PPh2C≡CR)}Pt(PPh3 )2J (M = Pt, R = Ph 4a, Tol 4b; M = Pd, R = Ph 5a, Tol 5b) and cis-[{(C≡CR′)2Pt(PPh2C≡CR)(μ-1κ P:2η2-PPh2C≡CR)}Pt(PPh3)2] (R′ = Ph, R = Ph 6a, Tol 6b; R′ = tBu, R = Ph 7a, Tol 7b), bearing only one PPh2C≡CR η2-coordinated to a Pt(0)(PPh3)2 fragment.
