TY - JOUR
T1 - Reactions of bis(iminophosphoranes) with palladium(II) dichloride
T2 - Metal-induced tautomerization orthopalladation and unexpected platinum-assisted [2 + 2] cycloaddition of an aryl-nitrile with a phosphinimine moiety
AU - Avis, Mandy W.
AU - Van Der Boom, Milko E.Der
AU - Elsevier, Cornelis J.
AU - Smeets, Wilberth J.J.
AU - Spek, Anthony L.
N1 - Funding Information:
This work was supported in pal"t (A.I,.S and W.J.J.S) by the Netherlands Foundation of Chemical Research (SON) with financial aid from the Netherhmds Orgaai° zation for Scientific Research (NWO). M.W.A. and C.J.E. wish to thank Professor K. Vrieze for support of this work and Professor K.V. Katti for use of the 500MHz NMR and other facilities during a stay of M.W.A at the University of Missouri-Columbia, USA.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 1997/1/11
Y1 - 1997/1/11
N2 - Reactions of bis(iminophosphoranyl)methane, CH2(PPh2=N-aryl)2, (BIPM; 1a,b) or 1,1-bis(iminophosphoranyl)ethane (1,1-BIPE; 1c) with Pd-and Pt-dichlorides containing weakly coordinating ligands (L) such as nitriles or cyclo-octadiene, afforded several products depending on the reaction time, type of ligand (1a-c) or nature of the metal. The first reaction observed is a metal-assisted tautomerization of BIPM to aryl-N=PPh2-CH=PPh2-NH-aryl. When BIPM reacts with PdCl2(L)2, exclusive formation of the C,N-chelate PdCl2{CH(PPh2=N-aryl)(PPh2-NH-aryl)} (2a,b) is observed, whereas with 1,1-BIPE (1c) a product mixture consisting of a C,N-chelate (2c) and an N,N′-chelate (3) is found. Orthometallation of the four-membered palladacycle (2) took place upon heating, giving the five-membered palladacycle [PdCl2{2-C6H4-PPh(NH[-pTol)-C′H-PPh2(NH-pTol)}-C,C′] (4). The molecular structure of 4 has been determined by X-ray crystallography. Reactions of BIPM (1a,b) with PtCl2(RC≡N)2 (R = phenyl, p-tolyl) afforded entirely different products: the six-membered platinacycles [PtCl(RC≡N){aryl-N=C(R)-N=PPh2-CH=PPb2-NH-aryl}-C,N]Cl (5) and [PtCl2{aryl-N=C(R)-N=PPh2-CH=PPh2-NH-aryl}-C,N] (6), due to an unexpected 2 + 2 cycloaddition of a nitrile with a P=N group.
AB - Reactions of bis(iminophosphoranyl)methane, CH2(PPh2=N-aryl)2, (BIPM; 1a,b) or 1,1-bis(iminophosphoranyl)ethane (1,1-BIPE; 1c) with Pd-and Pt-dichlorides containing weakly coordinating ligands (L) such as nitriles or cyclo-octadiene, afforded several products depending on the reaction time, type of ligand (1a-c) or nature of the metal. The first reaction observed is a metal-assisted tautomerization of BIPM to aryl-N=PPh2-CH=PPh2-NH-aryl. When BIPM reacts with PdCl2(L)2, exclusive formation of the C,N-chelate PdCl2{CH(PPh2=N-aryl)(PPh2-NH-aryl)} (2a,b) is observed, whereas with 1,1-BIPE (1c) a product mixture consisting of a C,N-chelate (2c) and an N,N′-chelate (3) is found. Orthometallation of the four-membered palladacycle (2) took place upon heating, giving the five-membered palladacycle [PdCl2{2-C6H4-PPh(NH[-pTol)-C′H-PPh2(NH-pTol)}-C,C′] (4). The molecular structure of 4 has been determined by X-ray crystallography. Reactions of BIPM (1a,b) with PtCl2(RC≡N)2 (R = phenyl, p-tolyl) afforded entirely different products: the six-membered platinacycles [PtCl(RC≡N){aryl-N=C(R)-N=PPh2-CH=PPb2-NH-aryl}-C,N]Cl (5) and [PtCl2{aryl-N=C(R)-N=PPh2-CH=PPh2-NH-aryl}-C,N] (6), due to an unexpected 2 + 2 cycloaddition of a nitrile with a P=N group.
KW - 2 + 2 cycloadditions
KW - Nitriles
KW - Palladium
KW - Phosphinimines
KW - Platinum
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U2 - 10.1016/S0022-328X(96)06684-3
DO - 10.1016/S0022-328X(96)06684-3
M3 - Article
AN - SCOPUS:0031564455
VL - 527
SP - 263
EP - 276
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-2
ER -