Reactivity of Pt(PR3)2 (R = cyclohexyl, CMe3) with sulfur dioxide and carbon disulfide

Interaction between d‐ and p‐Block Metals: Synthesis and Structure of Platinum–Alane Adducts

“…[15] Complex 2 crystallizes in the triclinic space group P1 , and the platinum center adopts an unusual Tshaped geometry with a P-Pt-P angle of 162.07(2)8. Similar geometries have only been reported for the related SO 2 complex trans-[(Cy 3 P) 2 Pt À SO 2 ] (P-Pt-P 165.72(4)8) [16] and the platinum(II) boryl complex trans-[(Cy 3 P) 2 Pt{B(Fc)Br}]-[BAr F 4 ] (Fc = [(h 5 -C 5 H 4 )Fe(C 5 H 5 )], Ar F = 3,5-C 6 H 3 (CF 3 ) 2 ; P-Pt-P 162.96(3)8). [17] The most prominent structural feature of 2 is the presence of an unsupported platinum-aluminum bond with a Pt-Al separation of 2.3857 (7) , which only slightly exceeds that of zerovalent platinum alanediyl complexes, for example, [(dcpe)Pt(AlCp*) 2 ] (dcpe = 1,2-bis(dicyclohexylphosphanyl)ethane, Cp* = Me 5 C 5 ; 2.327(2) and 2.335(2) ).…”

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

“…However, the attendant OS S = +3 and OS Rh = +2 in the complex would be difficult to reconcile with the diamagnetism of the compound, which is more in line with a Rh(I) (d 8 ) donating a pair of electrons to a neutral SO 2 ligand (OS S = +4). This is by no means unique, and SO 2 adducts with, for example, Pt(PR 3 ) 2 (R = cyclohexyl, tert-butyl) [317] or [PtX(C 6 H 2 {CH 2 N(CH 3 ) 2 } 2 -2,6-R-4)] (R = OH, X = Cl; R = H, X = Cl, Br, I) [318] are considered to contain respectively Pt(0) and Pt(II). Their reversible binding of SO 2 is more in accord with these OS than with ionic approximation towards Pt +2 The first structural identification of a TM → B donor-acceptor bond in the [Ru(CO)(P(C 6 H 5 ) 3 ){B(mt) 3 }] (B(mt) 3 = tris(methimazolyl)borane) metallaboratrane by Hill [321] in 1999 has rekindled interest in the field, which has seen spectacular progress in the intervening years when similar complexes of Co [322], Ni [323], and others have been synthesized.…”

Wechselwirkung zwischen d‐ und p‐Block‐Metallen: Synthese und Struktur von Platin‐Alan‐Addukten

“…Die ungewöhnliche T-förmige Struktur (P-Pt-P-Winkel 162.07(2)8) ähnelt bisher nur derjenigen des verwandten SO 2 -Komplexes trans-[(Cy 3 P) 2 Pt À SO 2 ] (P-Pt-P 165.72(4)8), [16] sowie des kationischen Platin(II)-Borylkomplexes trans- (3)8). [17] Ein auffallendes Strukturmerkmal von 2 ist die PlatinAluminium-Bindung, die nicht durch einen weiteren Brü-ckenliganden stabilisiert wird.…”