Inorganic Chemistry, Vol.34, No.22, 5461-5467, 1995
Reactivity of Deprotonated Mn-2(Mu-H)(Mu-Pcyh)(Co)(8) - Selective Monoauration to Mn-2(Mu-Aupr(3))(Mu-Pcyh)(Co)(8) and Mn-2(Mu-H)(Mu(3)-Pcy(Aupr(3)))(Co)(8) (R=cy, pH, P-C6H4F, P-C(6)H(4)OMe) and Kinetic-Studies of Their Conversion
In THF solution the dimanganese complex Mn-2(mu-H)(mu-PCyH)(CO)(8) (1) reacts with equimolar amounts of the non nucleophilic base DBU (1.8-diazabicyclo[5.4.0]undec-7-en) and ClAuPR(3) (R = Cy, Ph, p-C(6)H(4)OMe, p-C6H4F) at 20 degrees C within 1 h to afford the following mono- and diaurated pairs of isomers : Mn-2 mu-AuPR(3)(mu-PCyH)(CO)(8) (A) and Mn-2(mu-H)(mu(3)-PCy(AuPR(3)))(CO)(8) (B); Mn-2(mu-AuPR(3))(mu-PCy(AuPR(3)))(CO)(8) and Mn-2(AuPR(3))(2)(mu(4)-PCy)(CO)(8). Whereas we described the separated components of the last named pair in our previous publication, the monoaurated isomers are dicussed in this paper. These isomers have now been separated by a fractional crystallization procedure and identified by means of H-1 NMR, P-31 NMR, UV/vis, and v(CO) IR spectroscopic measurements. In the case of R = Ph, Mn-2(mu-AuPPh(3))(mu-PCyH)(CO)(8) (2) and Mn-2(mu-H)(mu(3)-PCY(AuPPh(3)))(CO)(8) (3) both crystallize triclinic, space group P ($) over bar 1, Z = 2 : 2, a = 10.687(2) Angstrom, b = 11.605(2) Angstrom, c = 14.369(2) Angstrom, alpha = 103.91(1)degrees, beta = 99.85(1)Angstrom, gamma = 93.97(1)degrees; 3, a = 12.741(1) A, b = 16.371(1)degrees Angstrom, c = = 9.068(2)degrees Angstrom, alpha = 97.85(1)degrees, beta = 110.73(1)degrees; gamma = 74.99(1)degrees. Both molecular structures show a common edge-sharing coordination bioctahedron with an orthogonal Mn-Mn bond. : Mn-2 mu-AuPR(3)(mu-PCyH)(CO)(8) (A) and Mn-2(mu-H)(mu(3)-PCy(AuPR(3)))(CO)(8) (B); Mn-2(mu-AuPR(3))(mu-PCy(AuPR(3)))(CO)(8) and Mn-2(AuPR(3))(2)(mu(4)-PCy)(CO)(8). Whereas we described the separated components of the last named pair in our previous publication, the monoaurated isomers are dicussed in this paper. These isomers have now been separated by a fractional crystallization procedure and identified by means of H-1 NMR, P-31 NMR, UV/vis, and v(CO) IR spectroscopic measurements. In the case of R = Ph, Mn-2(mu-AuPPh(3))(mu-PCyH)(CO)(8) (2) and Mn-2(mu-H)(mu(3)-PCY(AuPPh(3)))(CO)(8) (3) both crystallize triclinic, space group P ($) over bar 1, Z = 2 : 2, a = 10.687(2) Angstrom, b = 11.605(2) Angstrom, c = 14.369(2) Angstrom, alpha = 103.91(1)degrees, beta = 99.85(1)Angstrom, gamma = 93.97(1)degrees; 3, a = 12.741(1) A, b = 16.371(1)degrees Angstrom, c = = 9.068(2)degrees Angstrom, alpha = 97.85(1)degrees, beta = 110.73(1)degrees; gamma = 74.99(1)degrees. Both molecular structures show a common edge-sharing coordination bioctahedron with an orthogonal Mn-Mn bond.