ISSN:
1572-8862
Keywords:
Tungsten
;
isomeric forms
;
crystal structure
;
triple bonds
;
interconversion
Source:
Springer Online Journal Archives 1860-2000
Topics:
Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
,
Physics
Notes:
Abstract A thorough study of compounds with the formula W2Cl4(NHCMe3)2(PR3)2, withR 3=Me3, Et3, Prg n 3 Me2,Ph, is reported. In addition to the previously reported crystalline compounds, namely Ia,trans-W2Cl4(NHCMe3)2(PMe3)2 in space group Pmmn;3a,trans-W2Cl4(NHCM3)2(PEt3)2 in space group P21/a (or P21/c); and4,cis-W2Cl4(NHCMe3)2(PMe2Ph)2 in Pna21, we have obtained and structurally characterized the following new substances,1b,trans-W2Cl4,(NHCMe3)2(PMe2)2, space group P21/c,a= 12.233 (4) Å,b= 12.872 (4) Å,c=17.095 (5) Å,β=93.52 (2)°,Z=4,V=2687 (1) Å3 2,cis-W2Cl4(NHCMe3)2(PMe3)2, P21/c,a=9.673 (4) Å,b=17.249 (4) Å,c=16.244 (5) Å,β=99.63 (3),Z = 4 ,V=2669 (1) Å.3b,trans-W2Cl4(NHCMe3)2(PEt3)2, Pl,a=16.850 (3) Å,b=17.797 (3) Å,c= 11.459 (2)Å,α= 101.02 (1),β= 103.13°, y=84.23 (1)°,Z=4,V= 3279 (1) Å5,trans-W2Cl4(NHCM3)2(PMe2Ph)2, Fdd2,a=39.563 (8) Å at 20°C; 39.325 (10) Å at -6O°C,b = 57.543 (17) Å at 20°C; 57.186 (16) Å at -60°C,c= 8.810 (1) Å at 20°C; 8.770 (1) Å at - 60°C ,Z=24,V=20057 (7) Å3 (20°C), 19723 (8) Å3 ( - 60°C) .6,trans-W2Cl4(NHCMe3 2(PPrn 3)2, Pl,a= 17.287 (2) Å (20°C); 17.077 (5) Å (-60°C),b= 19.119 (2) Å (20°C); 18.952 (6) Å (-60°C),c= 12.713 (1) Å (20°C); 12.668 (4) Å (-60°C),Z=4,V= 3980 (1) Å3 (20°C), 3898 (2) ,Å3 ( - 60°C). In addition, the structure of3a was re-determined and refined so that the disorder ratio was a refined parameter, leading to a value of 0.520:0.480 instead of being arbitrarily fixed at 0.50:0.50. In all of the structures the molecules are held in eclipsed (but very distorted) rotational conformations and the W-W distances are all within the range of 2.305-2.330 Å. As will be shown in a later paper, for all phosphines, thecis andtrans isomers are of similar stability and an equilibrium mixture exists in solution. It is also shown that1a and3a do not contain unexpectedly short W-N bonds as previously reported.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01165490
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