Mononuclear Molybdenum(IV) Complexes with Two Multiply Bonded Chalcogen Ligands in Trans Configuration and Chelating Biphosphine Ligands
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- 作者：F. Albert Cotton and and Gü ; nter Schmid
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：May 21, 1997
- 年：1997
- 卷：36
- 期：11
- 页码：2267 - 2278
- 全文大小：283K
- 年卷期：v.36,no.11(May 21, 1997)
- ISSN：1520-510X
文摘
A series of molybdenum(IV) complexes of the typetrans-Mo(Q)(Q')(P
P)2 has beenprepared where Q and Q'are chalcogen ligands (O, S, Se, Te) and PP is eithercis-1,2-bis(diphenylphosphino)ethylene (dppee) or1,2-bis(diphenylphosphino)ethane (dppe). X-raycrystallographic studies were carried out to investigate howtheMo-Q distance is influenced by the mutually competitived
-p interactions between thepx and py orbitalsofthe chalcogen ligands and the dxz anddyz orbitals of the molybdenum center.trans-Mo(O)2(dppee)2(1) has beenprepared by the hydrolysis and deprotonation reaction of[Mo(O)(Cl)(dppee)2]Cl with NaOH inmethanol. Thecompounds where Q represents the heavier chalcogens (S, Se, Te) havebeen prepared by the reaction betweentrans-Mo(N2)2(PP)2and a chalcogen source:trans-Mo(S)2(dppee)2(2), BzS3Bz (dibenzyl trisulfide);trans-Mo(Se)2(dppee)2 (3),elemental Se;trans-Mo(Te)2(dppee)2(4), TePEt3 (Et = ethyl);trans-Mo(S)2(dppe)2(5),BzS3Bz;trans-Mo(Se)2(dppe)2(6), Se.trans-Mo(O)(S)(dppee)2(7) was obtained from the reaction ofMoCl3(THF)3 (THF = tetrahydrofuran), dppee, and NaHS in amixture of THF and methanol. The attemptedpreparationof 7 by the reaction of SO2 andtrans-Mo(N2)2(dppee)2yielded Mo(SO2)2(dppee)2(8). 1 crystallizes in themonoclinic space group P21/c (No. 14,Z = 2) with a = 11.1340(15) Å,b = 18.435(2) Å, c = 12.515(2) Å,and
= 110.999(9)
; 2 crystallizes in the triclinicspace group P
(No. 2, Z = 1) witha = 10.102(4) Å, b =10.722(4) Å, c = 12.195(3) Å, 
= 100.95(3), = 95.04(4), and 
= 117.81(2); 3crystallizes in the monoclinicspace group P21/c (No. 14,Z = 2) with a = 11.186(5) Å,b = 18.005(8) Å, c = 12.761(9) Å,and = 110.35(4); 4 crystallizes in the triclinic space groupP (No. 2, Z = 2) with a =12.681(4) Å, b = 19.280(5) Å, c=10.454(3) Å, = 104.60(2), =111.61(2), and = 75.12(2); 5crystallizes in the monoclinic space groupC2/c (No. 15, Z = 8) witha = 49.515(7) Å, b = 10.9286(12)Å, c = 18.203(3) Å, and = 98.306(12);6crystallizes in the monoclinic space group C2/c(No. 15, Z = 8) with a = 49.566(9) Å,b = 10.9765(15) Å,c = 18.282(3) Å, and = 98.541(13);7 crystallizes in the triclinic space groupP (No. 2, Z = 1) with a=10.040(1) Å, b = 10.563(1) Å, c =12.162(2) Å, = 75.30(1), = 85.93(1),and = 63.21(1); 8 crystallizesin the monoclinic space group C2/c (No. 15,Z = 4) with a = 21.534(6) Å,b = 12.4271(13) Å, c =19.550(5)Å, and = 118.480(14). The UV/vis and the31P{1H} NMR data for compounds1-7 are also reported anddiscussed.
P)2 has beenprepared where Q and Q'are chalcogen ligands (O, S, Se, Te) and PP is eithercis-1,2-bis(diphenylphosphino)ethylene (dppee) or1,2-bis(diphenylphosphino)ethane (dppe). X-raycrystallographic studies were carried out to investigate howtheMo-Q distance is influenced by the mutually competitived-p interactions between thepx and py orbitalsofthe chalcogen ligands and the dxz anddyz orbitals of the molybdenum center.trans-Mo(O)2(dppee)2(1) has beenprepared by the hydrolysis and deprotonation reaction of[Mo(O)(Cl)(dppee)2]Cl with NaOH inmethanol. Thecompounds where Q represents the heavier chalcogens (S, Se, Te) havebeen prepared by the reaction betweentrans-Mo(N2)2(PP)2and a chalcogen source:trans-Mo(S)2(dppee)2(2), BzS3Bz (dibenzyl trisulfide);trans-Mo(Se)2(dppee)2 (3),elemental Se;trans-Mo(Te)2(dppee)2(4), TePEt3 (Et = ethyl);trans-Mo(S)2(dppe)2(5),BzS3Bz;trans-Mo(Se)2(dppe)2(6), Se.trans-Mo(O)(S)(dppee)2(7) was obtained from the reaction ofMoCl3(THF)3 (THF = tetrahydrofuran), dppee, and NaHS in amixture of THF and methanol. The attemptedpreparationof 7 by the reaction of SO2 andtrans-Mo(N2)2(dppee)2yielded Mo(SO2)2(dppee)2(8). 1 crystallizes in themonoclinic space group P21/c (No. 14,Z = 2) with a = 11.1340(15) Å,b = 18.435(2) Å, c = 12.515(2) Å,and = 110.999(9); 2 crystallizes in the triclinicspace group P (No. 2, Z = 1) witha = 10.102(4) Å, b =10.722(4) Å, c = 12.195(3) Å, = 100.95(3), = 95.04(4), and = 117.81(2); 3crystallizes in the monoclinicspace group P21/c (No. 14,Z = 2) with a = 11.186(5) Å,b = 18.005(8) Å, c = 12.761(9) Å,and = 110.35(4); 4 crystallizes in the triclinic space groupP (No. 2, Z = 2) with a =12.681(4) Å, b = 19.280(5) Å, c=10.454(3) Å, = 104.60(2), =111.61(2), and = 75.12(2); 5crystallizes in the monoclinic space groupC2/c (No. 15, Z = 8) witha = 49.515(7) Å, b = 10.9286(12)Å, c = 18.203(3) Å, and = 98.306(12);6crystallizes in the monoclinic space group C2/c(No. 15, Z = 8) with a = 49.566(9) Å,b = 10.9765(15) Å,c = 18.282(3) Å, and = 98.541(13);7 crystallizes in the triclinic space groupP (No. 2, Z = 1) with a=10.040(1) Å, b = 10.563(1) Å, c =12.162(2) Å, = 75.30(1), = 85.93(1),and = 63.21(1); 8 crystallizesin the monoclinic space group C2/c (No. 15,Z = 4) with a = 21.534(6) Å,b = 12.4271(13) Å, c =19.550(5)Å, and = 118.480(14). The UV/vis and the31P{1H} NMR data for compounds1-7 are also reported anddiscussed.