Naphtholactam als Komplexligand

Naphtholactame as a Ligand Deprotonation of the fluorophore N‐Benz[cd]indol‐2(1H)‐on (= naphtholactame) with NaN(SiMe₃)₂ yields the naphtholactamate 1 , which is subsequently reacted with the chloro complexes [Ph₃PAuCl] and [(Ph₃P)₂PtCl₂]. The mono‐ and disubstitution products [Ph₃PAu(C₁₁H₆NO)] ( 2 ), [(Ph₃P)₂PtCl(C₁₁H₆NO)] ( 3 ) and [(Ph₃P)₂Pt(C₁₁H₆NO)₂] ( 4 ) with one ( 2 , 3 ) or two ( 4 ) metal‐N‐bonds respectively, were isolated. Substitution of chloride in the phosphanes Ph_3‐nPCl_n with 1 leads to the naphtholactamato‐N‐phosphane derivatives Ph_3‐nP(C₁₁H₆NO)_n (n = 3 ( 5 ), 2 ( 6 ), 1 ( 7 )). 7 , which is particularly sensitive towards air oxygen, is readily oxidized to give the corresponding phosphane oxide Ph₂P(O)(C₁₁H₆NO) ( 8 ). The ligating properties of 5 and 7 have been examined. In a two‐step reaction HAuCl₄, C₄H₈S (= THT) and 7 yield the phosphane complex [{Ph₂(C₁₁H₆NO)P}AuCl] ( 9 ). Photolytic activation of W(CO)₆ in THF and subsequent addition of 5 or 7 surprisingly leads to the tetracarbonyl complexes $[(CO)_{4}overline{W{P(C_{11}H_{6}NO)_{2}(C_{11}H_{6}NO)}]}$/ ( 10 ) and $[(CO)_{4}overline{W{PPh_{2}(C_{11}H_{6}NO)}]}$/ ( 11 ), respectively. Both exhibit a bidentate P, O‐bound naphtholactamatophosphane ligand. The compounds have been characterized by their IR‐, NMR‐ and Mass spectra, compound 11 additionally by a single crystal structure analysis. Theoretical studies on PM3‐level for 5 , including a structure optimization and as well as an NBO analysis, have been carried out.