含环偶磷氮烷配体的羰基铁衍生物的合成和晶体结构

Synthesis and Crystal Structures of Carbonyl Iron Derivatives Containing Cyclodiphosphazane Ligand

用Fe3 (CO) 12 与顺 2 ,4 二 (叔丁基胺基 ) 1,3 二 (叔丁基 ) 1,3 ,2 ,4 环偶磷氮烷cis [P(NHBu t)NBu t] 2 (L)反应 ,得到两个新的含偶磷氮环的单核羰基铁衍生物 :Fe(CO) 4 [{P(NHBu t)NBu t}2 ] ( 1)和Fe(CO) 4 [P(NHBu t) (NBu t) 2 P(O)H ]( 2 ) .对它们进行了元素分析 ,IR和1HNMR谱表征 ,并用X ray单晶衍射法测定了晶体结构 .1:正交晶系 ,Pna2 ( 1)空间群 ,a =1.70 3 8( 9)nm ,b =0 .885 6( 5 )nm ,c =3 .5 65 9( 18)nm ,V =5 .3 81( 5 )nm3 ,Dc=1.2 75g/cm3 ,Z =8.2 :单斜晶系 ,P2 ( 1) /n空间群 ,a =0 .9999( 2 )nm ,b =1.44 76( 3 )nm ,c =1.5 5 5 9( 3 )nm ,β =92 .40 ( 3 )° ,V =2 .2 5 0 4( 8)nm3 ,Dc=1.3 61g/cm3 ,Z =4.在两个羰基铁化合物中 ,配位基偶磷氮烷环以单齿P原子与Fe原子配位 .2中 ,未配位P(III)被氧化成具有膦酰基结构 [P(O)H]的P(V) .

The reaction of Fe-3(CO)12 with cis -2,4-di ( tert-butylamino) -1, 3-di ( tert-butyl) - 1, 3,2,4-cyclodiphosphazane ( L), yielded two novel mononuclear carbonyl iron derivatives containing cyclodiphosphazane ligand, Fe(CO)(4) [{P(NHBu-t)NBu-t}(2)] (1) and Fe(CO)(4)[P(NHBu-t) (NBu-t)(2)P(O)H] (2). These compounds were characterized by elemental analysis, IR and H-1 NMR spectra, and the structures of 1 and 2 were determined by single-crystal X-ray diffraction. 1: orthorhorribic, Pha2(1), a = 1.7038(9) nm, b =0.8856(5) nm, c = 3.5659 (18) rim, V = 5.381(5) nm(3), D-c = 1. 275 g/cm(3) Z = 8. 2: monoclinic, P2(1)/n, a = 0. 9999(2) ran, b = 1.4476(3) nm, c = 1.5559(3) nm, beta=92.40(3)degrees, V=2.2504(8) nm(3), D-c = 1.361 g/cm(3), Z =4. In the two carbonyl iron derivatives, the phosphorus-nitrogen heterocycles were not cleaved during the reaction, and one P atom of them was coordinated to Fe atom. In the compound 2, another P(III) atom was oxidized to the P(V), phosphonic amide P(O) H, in which the bond between P and NHBu-t group was cleaved and one P-H bond was formed.