Discrete and Polymeric Organometallic‐Organic Hybrid Materials Based on the Diphosphorus Complex [Cp 2 Mo 2 (CO) 4 (η 2 ‐P 2 )], Cu I Salts, and 2,2′‐Bipyrimidine

The reaction of the diphosphorus complex [Cp 2 Mo 2 (CO) 4 (η 2 ‐P 2 )] ( 1 ), with the Cu I salts [Cu(CH 3 CN) 4 ][BF 4 ] or [Cu(CH 3 CN) 4 ][PF 6 ], and a mixture of [Cu(CH 3 CN) 4 ][BF 4 ] and CuCl in the presence of 2,2′‐bipyrimidine ( 2 ) is studied. Depending on the Cu I salts used and the layering solvent involved in the crystallisation, a variety of novel coordination compounds are accessible in moderate to excellent yields (26–80 %): the novel dicationic molecular organometallic‐organic hybrid complexes [{Cp 2 Mo 2 (CO) 4 (µ 3 ,η 1:2:2 ‐P 2 )} 4 (µ 2 ,η 1:1:1:1 ‐C 8 H 6 N 4 )Cu 2 ][BF 4 ] 2 ( 3 ) and [{Cp 2 Mo 2 (CO) 4 (µ 3 ,η 1:2:2 ‐P 2 )} 2 {Cp 2 Mo 2 (CO) 4 (µ 3 ,η 2:2:2 ‐P 2 )} 2 (µ 2 ,η 1:1:1:1 ‐C 8 H 6 N 4 )Cu 2 ][PF 6 ] 2 ( 4 ), the unique neutral 1D organometallic‐organic hybrid polymer [{Cp 2 Mo 2 (CO) 4 (µ 4 ,η 1:1:2:2 ‐P 2 )} 2 (µ 2 ,η 1:1:1:1 ‐C 8 N 6 N 4 )(CuCl) 2 ] n ( 5 ) and the unprecedented 2D organometallic‐organic hybrid polymer [{Cp 2 Mo 2 (CO) 4 (µ 4 ,η 1:1:2:2 ‐P 2 )}(µ 2 ,η 1:1:1:1 ‐C 8 H 6 N 4 ){Cu 2 (µ‐Cl)}] 2 [BF 4 ] 2 n ( 6 ).