Synthetic and structural studies on organotransition metal–bismuth nitrates

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…The analogous [{Cp(CO) 2 Mo} 2 Bi(SCN)] also crystallises in a polymeric array, in this case supported by intermolecular Bi· · ·NCS-Bi interactions, resulting in a similar four-coordinate disphenoidal geometry about Bi, with the Bi-S and Bi· · ·N interactions at the axial sites [60]. [{Cp(CO) 3 Mo} 2 Bi(ONO 2 )] has also been reported, and can be assumed to adopt a polymeric structure in analogy with the corresponding, structurally characterised iron species [59].…”

“…Examples are provided by the studies on transition metal-bismuth nitrates [(NO 3 )Bi(ML n ) 2 ], which can be synthesised by Bi(NO 3 ) 3 ·5H 2 O and the corresponding metallate [59]. The chloride can also be exchanged for a thiocyanate by the use of a source of Bi(SCN) 3 as the starting material [60].…”

“…The drive to synthesise exciting structural types gave rise to a spiro-cluster [{Ru 2 (CO) 8 }( 4 -Bi){(-H)Ru 3 (CO) 10 }] (53) [149], cubane-like clusters such as 54 [59,150,151] and large clusters like [PPN] 2 [Bi 4 Co 9 (CO) 8 (-CO) 8 8 ]·1.08THF [152] (Fig. 15).…”

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

“…815 The nitrate compounds [Bi(NO 3 ){M(CO) 3 Cp} 2 ] (M = Cr, Mo, W) have also been made. 816 Yields are generally good, though even here the outcome is not always predictable, for example the isolation o f the cluster [Mo 5 (CO) 14 (u4-Sb) 2 Cp 4 ] f r o m the reaction of SbCl 3 with [Mo(CO) 3 Cp] . 1 7 On photolysis or thermolysis, the complex [BiCl{Mo(CO) 3 Cp} 2 ] is converted into the dibismuth compound [Mo 2 (CO) 4 (u-Bi 2 )Cp 2 ], analogous to the u-P 2 and u-As 2 species described above, 814 ' 818 while treatment with S(TMS) 2 gives a compound with a bridging BiS unit.…”

Heterocyclic Bismuth(III) Dithiocarbamato Complexes as Single‐Source Precursors for the Synthesis of Anisotropic Bi2S3 Nanoparticles

“…[27] The BiÀOb ond lengths average2 .79(7) a nd are longer than those reported for the monodentate nitrato li-gands (h 1 -NO 3 À ), for example, bis(nitrato)(methanol){N-phenyl-N'-[1-(pyrazin-2-yl)ethylidene]carbamohydrazonothioato}bismuth(III),w hich are distinctly non-bridging (BiÀO, 2.45(6) ). More specifically,o nly three crystallographicallyc haracterised examples of complexes with linking m 2 -nitrato-O,O' ligands,B i ÀO(NO)O'ÀBi, are known:t he room-temperature structure of 1, [26] catena-{(m 2 -nitrato-O,O')-bis[(h 5 -cyclopentadienyl)dicarbonyliron(II)]bismuth(III)} [29] and the Bi III -Nd III heterome- Bi (1) (2) 2.6456 (14) Bi (2) (11) Bi (1) 4 (m 3 -cydta)Bi-(m-ONO 2 )]·2.5 H 2 O} n ,w here cydta is trans-cyclohexylene-1,2-diaminetetraacetate. More specifically,o nly three crystallographicallyc haracterised examples of complexes with linking m 2 -nitrato-O,O' ligands,B i ÀO(NO)O'ÀBi, are known:t he room-temperature structure of 1, [26] catena-{(m 2 -nitrato-O,O')-bis[(h 5 -cyclopentadienyl)dicarbonyliron(II)]bismuth(III)} [29] and the Bi III -Nd III heterome- Bi (1) (2) 2.6456 (14) Bi (2) (11) Bi (1) 4 (m 3 -cydta)Bi-(m-ONO 2 )]·2.5 H 2 O} n ,w here cydta is trans-cyclohexylene-1,2-diaminetetraacetate.…”