CRYSTAL-STRUCTURES OF (MEC5H4)3M(L) (M = URANIUM OR CERIUM - L = QUINUCLIDINE OR P(OCH2)3CET) - EVIDENCE FOR URANIUM TO PHOSPHORUS PI-BACK-BONDING
CRYSTAL-STRUCTURES OF (MEC5H4)3M(L) (M = URANIUM OR CERIUM - L = QUINUCLIDINE OR P(OCH2)3CET) - EVIDENCE FOR URANIUM TO PHOSPHORUS PI-BACK-BONDING
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DOI：
10.1021/om00096a016
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发表时间：
1988-06-01
期刊：
影响因子：
2.8
通讯作者：
ZALKIN, A
中科院分区：
文献类型：
--
作者：
BRENNAN, JG;STULTS, SD;ZALKIN, A
描述了(MeC/sub 5/H/sub 4/)/sub 3/M(L)的合成和x射线晶体结构，其中M为Ce或U， L为N(CH/sub 2/CH/sub 2/)/sub 3/CH或P(OCH/sub 2/)/sub 3/CEt。（MeC/sub - 5/H/sub - 4/）/sub - 3/U（N(CH/sub - 2/CH/sub - 2/)/sub - 3/CH）和(MeC/sub - 5/H/sub - 4/)/sub - 3/Ce（N(CH/sub - 2/CH/sub - 2/)/sub - 3/CH）晶体是空间群P - 1的三斜晶体，Z = 2。对于铀配合物，a = 10.604 (4) a, b = 13.552 (6) a, c = 8.333 (4) a，…= 100.20 (4)/sup 0/，…= 74.78 (4)/sup 0/，和…= 104.13 (4)/sup 0/ at 23/sup 0/C；计算密度为1.751 g/cm/sup 3/。对于铈化合物，a = 10.609 (4) a, b = 13.586 (5) a, c = 8.348 (5) a，…= 100.15 (4)/sup 0/，…= 74.75 (4)/sup 0/，和…= 104.01 (3)/sup 0/ at 23/sup 0/C；计算密度为1.451 g/cm/sup 3/。铀（III）和铈（III）原子分别与三个环戊二烯环相连；U-C和Ce-C的平均距离分别为2.82 +/- 0.03 A和2.85 +/- 0.03 A。U-N和Ce-N距离分别为2.764 (4)A和2.789 (3)A。（MeC/sub - 5/H/sub - 4/）/sub - 3/U（P(OCH/sub - 2/)/sub - 3/CEt）和(MeC/sub - 5/H/sub - 4/)/sub - 3/Ce（P(OCH/sub - 2/)/sub - 3/CEt）晶体是空间群P2/sub - 1/2/sub - 1/ sub - 1/ Z = 4的正交体。用单晶x射线衍射法测定了两种同形配合物的结构。对于铀配合物，在23/sup 0/ c时，a = 13.122 (5) a, b = 16.363 (5) a, c = 10.922 (4) a；计算密度为1.806 g/cm/sup 3/。对于铈配合物，在23/sup 0/ c时，a = 13.163 (7) a, b = 16.443 (7) a, c = 10.976 (4) a；计算密度为1.509 g/cm/sup 3/。金属原子四面体地与三个环戊二烯环和一个磷原子结合。U-P距离为2.988 (6)A， Ce-P距离为3.086 (3)A；U-C和Ce -C的平均距离分别为2.80 +/- 0.05和2.82 +/- 0.03 A。
The synthesis and X-ray crystal structure of (MeC/sub 5/H/sub 4/)/sub 3/M(L), where M is Ce or U and L is N(CH/sub 2/CH/sub 2/)/sub 3/CH or P(OCH/sub 2/)/sub 3/CEt, are described. Crystals of (MeC/sub 5/H/sub 4/)/sub 3/U(N(CH/sub 2/CH/sub 2/)/sub 3/CH) and (MeC/sub 5/H/sub 4/)/sub 3/Ce(N(CH/sub 2/CH/sub 2/)/sub 3/CH) are triclinic of space group P anti 1 with Z = 2. for the uranium complex, a = 10.604 (4) A, b = 13.552 (6) A, c = 8.333 (4) A, ..cap alpha.. = 100.20 (4)/sup 0/, ..beta.. = 74.78 (4)/sup 0/, and ..gamma.. = 104.13 (4)/sup 0/ at 23/sup 0/C; the calculated density is 1.751 g/cm/sup 3/. For the cerium compound, a = 10.609 (4) A, b = 13.586 (5) A, c = 8.348 (5) A, ..cap alpha.. = 100.15 (4)/sup 0/, ..beta.. = 74.75 (4)/sup 0/, and ..gamma.. = 104.01 (3)/sup 0/ at 23/sup 0/C; the calculated density is 1.451 g/cm/sup 3/. The uranium(III) and cerium(III) atoms are each bonded to three cyclopentadienyl rings; the average U-C and Ce-C distances are 2.82 +/- 0.03 and 2.85 +/- 0.03 A, respectively. The U-N and Ce-N distances are 2.764 (4) and 2.789 (3) A, respectively. Crystals of (MeC/sub 5/H/sub 4/)/sub 3/U(P(OCH/sub 2/)/sub 3/CEt) and (MeC/sub 5/H/sub 4/)/sub 3/Ce(P(OCH/sub 2/)/sub 3/CEt) are orthorhombic of space group P2/sub 1/2/sub 1/2/sub 1/ with Z = 4. The structure of the two isomorphous complexes were determined by single-crystal X-ray diffraction methods. For the uranium complex, a = 13.122 (5) A, b = 16.363 (5) A, c = 10.922 (4) A at 23/sup 0/C; the calculated density is 1.806 g/cm/sup 3/. For the cerium complex, a = 13.163 (7) A, b = 16.443 (7) A, and c = 10.976 (4) A at 23/sup 0/C; the calculated density is 1.509 g/cm/sup 3/. The metal atom is tetrahedrally bound to the three cyclopentadienyl rings and a phosphorus atom. The U-P and Ce-P distances are 2.988 (6) and 3.086 (3) A, respectively; the average U-C and Ce C distances are 2.80 +/- 0.05 and 2.82 +/- 0.03 A, respectively.