Abstract: | Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. Co4P2(PtBu2)2(CO)8] and {Co(CO)3}2P4tBu4] from Co2(CO)8 and tBu2P–P=P(Me)tBu2 Co2(CO)8 reacts with tBu2P–P=P(Me)tBu2 yielding the compounds Co4P2(PtBu2)2(CO)8] ( 1 ) and {η2tBu2P=P–P=PtBu2}{Co(CO)3}2] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ2‐bridged by tBu2P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)3 units is η2‐coordinated to the terminal P2 units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P21/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°. |