Toward Frameworks with Multiple Aligned and Interactive Fe(CO) 3 Rotators: Syntheses and Structures of Diiron Complexes Linked by Two trans -Diaxial α,ω-Diphosphine Ligands Ar 2 P(CH 2 ) n PAr 2
Toward Frameworks with Multiple Aligned and Interactive Fe(CO) 3 Rotators: Syntheses and Structures of Diiron Complexes Linked by Two trans -Diaxial α,ω-Diphosphine Ligands Ar 2 P(CH 2 ) n PAr 2
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具有多个对齐和相互作用的 Fe(CO) 3 旋转体的框架：由两个反式双轴α,β-二膦配体 Ar 2 P(CH 2 ) n PAr 2 连接的狄铁配合物的合成和结构
DOI：
10.1021/acs.inorgchem.0c03737
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发表时间：
2021
影响因子：
4.6
通讯作者：
Gladysz, John A.
中科院分区：
文献类型：
--
作者：
Zarcone, Samuel R.;Chu, Gong M.;Ehnbom, Andreas;Cardenal, Ashley;Fiedler, Tobias;Bhuvanesh, Nattamai;Hall, Michael B.;Gladysz, John A.
(η4-亚苄基丙酮)Fe(CO)3与α,ω-二膦Ar2P(CH2)nPAr2反应得到三角双锥二铁四磷配合物trans,trans-(CO)3Fe[Ar2P(CH2)nPAr2]2Fe(CO)3(n/Ar = 3/Ph3, 4/Ph4a, 4/p-tol4b; 56–19%）。晶体结构建立基本平行的 P-Fe-P 轴，铁-铁距离为 5.894(9)–5.782(1) Å (3) 和 6.403(1)–6.466(1) Å (4a,b)，Fe(CO)3 旋转器的范德华半径为 4.45 Å，其平面偏移 0.029–1.665 Å。 Ph2P(CH2)6PPh2 的类似反应产生方锥体单铁络合物反式-(CO)3Fe[Ph2P(CH2)6PPh2] (6′, 31%)，这是二膦跨越基底位置的罕见情况(∠P–Fe–P 147.4(2)°)。 3 和 6' 在室温下都表现出两个 CO13C NMR 信号，表明 NMR 时间尺度上的缓慢交换，在前者中可能需要 Fe(CO)3/Fe(CO)3 齿轮。在类似条件下，4a，b 显示一个信号。研究了之前报道的 Fe(CO)3 和 Ph2P(CH2)nPPh2 的加合物 (1:1,n= 1–5; 2:2,n= 5)，并借助 DFT 计算分析了所有配合物的 IR νCeqOband 模式和能量。从热力学角度看，二铁配合物是优选的。注意限制二铁配合物中 Fe(CO)3/Fe(CO)3 相互作用的类型。
Reactions of (η4-benzylideneacetone)Fe(CO)3and the α,ω-diphosphines Ar2P(CH2)nPAr2afford the trigonal bipyramidal diiron tetraphosphorus complexestrans,trans-(CO)3Fe[Ar2P(CH2)nPAr2]2Fe(CO)3(n/Ar = 3/Ph3, 4/Ph4a, 4/p-tol4b; 56–19%). Crystal structures establish essentially parallel P–Fe–P axes, iron–iron distances of 5.894(9)–5.782(1) Å (3) and 6.403(1)–6.466(1) Å (4a,b), and van der Waals radii of 4.45 Å for the Fe(CO)3rotators, the planes of which are offset by 0.029–1.665 Å. Analogous reactions of Ph2P(CH2)6PPh2yield the square pyramidal monoiron complextrans-(CO)3Fe[Ph2P(CH2)6PPh2] (6′, 31%), a rare case where a diphosphine spanstransbasal positions (∠P–Fe–P 147.4(2)°). Both3and6′exhibit two CO13C NMR signals at room temperature, indicating slow exchange on the NMR time scale, which in the former could entail Fe(CO)3/Fe(CO)3gearing. Under analogous conditions,4a,bexhibit one signal. Previously reported adducts of Fe(CO)3and Ph2P(CH2)nPPh2are surveyed (1:1,n= 1–5; 2:2,n= 5), and the IR νC≡Oband patterns and energies of all complexes analyzed with the aid of DFT calculations. The diiron complexes are preferred thermodynamically. Attention is given to limiting types of Fe(CO)3/Fe(CO)3interactions in the diiron complexes.