AbstractThe reaction of CuO'Bu with CO2, and iPr2NH in the presence of PPh3, gives the dialkylcarbamato complex [Cu(O2CNiPr2)(PPh3)2] (1). The CO2/R2NH system (R = Me, Et) in an appropriate organic medium reacts with Ag2O giving the corresponding N,N‐dialkylcarbamato complexes of analytical formula [Ag(C2CNR2)] (R = Me, 2; R = Et, 3). The methyl derivative 2 was characterized by X‐ray diffraction methods. Crystal data of 2: for [Ag2(O2CNMe2)2], C6H12Ag2N2O4, mol. wt. 391.9; monoclinic, space group P21/c, a = 12.08(1), b = 3.797(2), c = 11.316(7) Å, β = 113.37(6)°, V = 476.3 Å3, Z = 2, Dc = 2.732 g cm−3; μ(MoKα) = 40.64 cm−1, F(000) = 376.0; R = 0.059, Rw = 0.067; g.o.f. 1.27. The structure consists of dinuclear [(Ag2OCNMe2)2] units with slightly distorted linearly two‐coordinated Ag‐atoms containing bridging carbamato groups to form a substantially planar eight‐membered ring with an intra‐annular AgAg distance of 2.837(2) Å; the dinuclear units are further joined by AgO bonds to form an infinite array. Compound 3, which is presumably dinuclear, as suggested by cryoscopic measurements in benzene, undergoes a structural fission with PPh3, giving the mononuclear triphenylphosphine derivative [Ag(O2CNEt2)(PPh3)2] (4). The amine‐catalyzed conversion of Ag2O into Ag2CO3, in the presence of the iPr2NH/CO2 system, is also reported. Cl‐Exchange from [AuCl(PPh3)] with [Ag(O2CNEt2)] (3) gives the first N,N‐dialkylcarbamato complex of gold, namely [Au(O2CNEt2)(PPh3)] (5), which crystallizes in the monoclinic system: C23H25AuNO2P · 0.5 C7H16, mol. wt. 625.5, space group P21/c; a = 13.212(5), b = 12.25(1), c = 16.795(6) Å, β = 109.09(2)°, V = 2568(2) Å3, Z = 4, Dc, = 1.618 g cm−3; μ(AgKα) = 31.40 cm−1, F(000) = 1236.0; R = 0.058; Rw = 0.064; g.o.f. 2.121. The compound contains two‐coordinated Au‐atom, namely to the P‐atom and to the O‐atom of the monodentate carbamato group, the PAuO bond angle being 174.7(3)°. The reaction with MeI showed these compounds to react predominantly at the carbamato O‐atom giving the corresponding urethanes R2NCO2Me. Evidence was gathered for the transient coordination of CO to Ag in 3.