TY - JOUR
T1 - Activation of arylnitroso substrates on a platinum-germylene complex facilitating the formation of new N-C and N-S bonds
AU - Litz, Kyle E.
AU - Kampf, Jeffrey W.
AU - Banaszak Holl, Mark M.
PY - 1998/8/5
Y1 - 1998/8/5
N2 - The reaction of (Et3P)2PtGe[N(SiMe2)2]2 (1) with nitrosobenzene and 2-nitrosotoluene yields (Et3P)2-PtN(Ph)OGe[N(siMe3)2]2 (3a) and (Et3P)2PtN(o-Tol)OGe[N(SiMe3)2]2 (3b), respectively. The reactivity of 3a with SO2, H2CO, CO2, and PhNCO was explored yielding the five-membered heterocyclic complex (Et3P)2- PtS(O)2N(Ph)OGe[N(SiMe3)2]2 (6a) and the six-membered heterocyclic complexes (Et3P)2PtOC(H)2N(Ph)OGe[N(SiMe3)2]2 (7a), (Et3P)2PtoC(O)N(Ph)OGe [N(SiMe3)2]2 (8a), and (Et3P)2PtN(Ph)C(O)N(Ph)C(O)N(Ph)OGe- [N(SiMe3)2]2 (9a), respectively. The structures of 3a, 6a, 7a, and 9a were determined by single-crystal X-ray diffraction. 3b was observed to react in a fashion similar to 3a as demonstrated by reactions with SO2 and H2CO which gave (Et3P)2PtS(O)2N(o-Tol)OGe[N(SiMe3)2]2 (6b) and (Et3P)2PtOC(H)2N(o-Tol)OGe[N(SiMe3)2]2 (7b). Complexes 6a and 6b represent the first isolated and characterized examples of metal-stabilized -S(O)2N-(R)O- fragments, the isoelectronic analogue of an elusive intermediate proposed as the first step in Contact Process for the oxidation of SO2 by platinum catalysts. As a group, the reactions in this paper demonstrate the cooperative ability of metal-germylenes to activate unsaturated organic substrates and promote their subsequent chemical modification, while avoiding scission of the Pt-Ge bond.
AB - The reaction of (Et3P)2PtGe[N(SiMe2)2]2 (1) with nitrosobenzene and 2-nitrosotoluene yields (Et3P)2-PtN(Ph)OGe[N(siMe3)2]2 (3a) and (Et3P)2PtN(o-Tol)OGe[N(SiMe3)2]2 (3b), respectively. The reactivity of 3a with SO2, H2CO, CO2, and PhNCO was explored yielding the five-membered heterocyclic complex (Et3P)2- PtS(O)2N(Ph)OGe[N(SiMe3)2]2 (6a) and the six-membered heterocyclic complexes (Et3P)2PtOC(H)2N(Ph)OGe[N(SiMe3)2]2 (7a), (Et3P)2PtoC(O)N(Ph)OGe [N(SiMe3)2]2 (8a), and (Et3P)2PtN(Ph)C(O)N(Ph)C(O)N(Ph)OGe- [N(SiMe3)2]2 (9a), respectively. The structures of 3a, 6a, 7a, and 9a were determined by single-crystal X-ray diffraction. 3b was observed to react in a fashion similar to 3a as demonstrated by reactions with SO2 and H2CO which gave (Et3P)2PtS(O)2N(o-Tol)OGe[N(SiMe3)2]2 (6b) and (Et3P)2PtOC(H)2N(o-Tol)OGe[N(SiMe3)2]2 (7b). Complexes 6a and 6b represent the first isolated and characterized examples of metal-stabilized -S(O)2N-(R)O- fragments, the isoelectronic analogue of an elusive intermediate proposed as the first step in Contact Process for the oxidation of SO2 by platinum catalysts. As a group, the reactions in this paper demonstrate the cooperative ability of metal-germylenes to activate unsaturated organic substrates and promote their subsequent chemical modification, while avoiding scission of the Pt-Ge bond.
UR - http://www.scopus.com/inward/record.url?scp=0032486804&partnerID=8YFLogxK
U2 - 10.1021/ja980888f
DO - 10.1021/ja980888f
M3 - Article
AN - SCOPUS:0032486804
SN - 0002-7863
VL - 120
SP - 7484
EP - 7492
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 30
ER -