Table1Syntheticandanalyticaldataofoxime-modified phenylimidovanadium(V)complexes

S. No. /

Complex

/ Yield*
(%) / PriOH (gm.)
Obs.
(Calcd.) / Colour and
Physical State / Analyses (%)
Obs. (Calcd.) / M. Pt.
(°C)
OPri / V / N
1 / [V(NPh)(OiPr)2{(ONC)(CH3)(C4H3O-2)}]
(1) / 97 / 0.11
(0.12) / Brown solid / 30.67
(30.75) / 13.15
(13.25) / 7.10
(7.29) / 120
2 / [V(NPh)(OiPr){(ONC)(CH3)(C4H3O-2)}2]
(2) / 98 / 0.19
(0.24) / Brown solid / 13.08
(13.15) / 11.25
(11.34) / 9.26
(9.35) / 108
3 / [V(NPh){(ONC)(CH3)(C4H3O-2)}3]
(3) / 98 / 0.51
(0.58) / Brown solid / - / 9.82
(9.90) / 10.82
(10.89) / 110

* Crude Yield

Table2 SomeimportantIRspectraldata(cm­1)ofoxime-modifiedphenylimidovanadium(V)complexes

Complex / ν (C=N) / ν (C-O) / ν (V=N) / ν (N-O) / ν (V-O) / ν (V-N)
[V(NPh)(OiPr)2{(ONC)(CH3)(C4H3O-2)}]
(1) / 1585s / 1065s / 968vs / 902vs / 575vs, 524vs / 470vs
[V(NPh)(OiPr){(ONC)(CH3)(C4H3O-2)}2 ]
(2) / 1586m / 1075m / 1000m / 908m / 570m, 546 m / 502m
[V(NPh){(ONC)(CH3)(C4H3O-2)}3]
(3) / 1562s / 1085m / 1000m / 900m / 562m / 465m

Table 31H, 13C and 51V NMR data (ppm) of oxime-modifiedphenylimidovanadium(V) complexes

Complex / 1H NMR / 13C NMR / 51V NMR

(1) / 1.34(d,J=6.0Hz,12H,CH3­OiPr);2.29(s,3H,CH3­oxime);5.06(sep,J=6.0Hz,2H,CH­OiPr);6.34(dd,J=1.8Hz,1H,H­4);6.76(m,1H,H­3);6.98-7.23(m,5H,H-β,H­γ& H-δ);7.30 (m, 1H, H-5) / 14.1(CH3-oxime);25.5(CH3- OiPr);81.9(CH­OiPr);109.4(C­4);112.0(C­3);126.0(C­β);126.2(C­γ);127.8(C­δ);138.3(C-2);143.0(C­5);149.8(C=N) / -615.4
(2) / 1.34(d,J=6.0Hz,6H,CH3­OiPr);2.33(s,3H,CH3­oxime);5.09(sep,J=6.0 Hz,1H,CH­OiPr);6.34(m,2H,H­4);6.62(m,2H,H­3);6.83­7.17(m,5H, H-β, H-& H-δ); 7.43(m, 2H, H-5) / 14.3(CH3­oxime);25.5(CH3­ OiPr);82.0(CH­OiPr);109.4(C­4);112.02(C­3);126.0(C­β);126.2(C­γ);129.2(Cδ);138.4(C­α);138.8(C­2);143.8(C­5);149.8(C=N) / -615.6

(3) / 2.40(s,9H,CH3­oxime);6.41(m,3H,H­4);6.71(m,3H,H­3);6.81­7.26(m,5H,H­β,H­H­δ);7.45(m, 3H, H-5) / 14.3(CH3­oxime);111.0(C­4);112.0(C­3);118.3(C­β); 128.3(C­γ);129.2(C­δ);138.9(C­);143.6(C­2);143.9(C­5);148.9(C=N) / -615.1

Table4Fragmentedmolecularionsvsm/evaluesof[V(NPh){(ONC)(CH3)(C4H3O-2)}3] (3)

Complex / Fragmented ions / m/z value
[V(NPh){(ONC)(CH3)(C4H3O-2)}3]
(3) / V(NC6H5){ONC(CH3)(C4H3O)}{ONC2(C4H3O)}{ONC(C4H3O)}+
V(NC6H5){ONC(CH3)(C4H3O)}{NC(C4H3O)}{ONC(C4H3O)}+
V(NC6H5){NC2(C4H3O)}{NC(C4H3O)}{ONC(C4H3O)}+
V(NC6H5){ONC(CH2)(C4H3O)}{(C4H3O)}{ON(C4H3O)}+
V(NC6H5){NC(OH)}{ONC(CH3)(C4H3O)}{ONC(C4H3O)}+
V(NC6H5){NC(OH)}{ON(C4H3O)}{ONC(C4H3O)}+
V(NC6H5){(C4H3O)}{C(CH2)(C4H3O)}{N(C4H3O)}+
V(NC6H5){(C4H3O)}{C(C4H3O)}{N(C4H3O)}+
V(NC6H5){(C4H3O)}{(CH)(C4H3O)}{(C4H3O)}+
V(NC6H5){NC(OH)}{NO(CH3)}{ON(CH)(C4H3O)}+
V(NC6H5){N(OH)}{NO(CH3)}{ONC(C4H3O)}+
V(NC6H5)(NC)(NO){ONC(C4H3O)}+
V(NC6H5){N(CH2)(OH)}{ON(CH3)} {ONC(CH3)}+
V(NC6H5) (ON){ONC(C4H3O)}+
V(NC6H5){NC(OH)}{ON(CH3)}{ N (OH) }+
V(NC6H5)(NC)(NO)(ONC) +
V(NC6H5){C(C4H3O)}+
V(NC6H5)(C)(OH)(ONC)+
V(NC6H5)(C3HO)+
V(NC6H5)(C2H)+
V(NC6H5)(C)+
V(CH)(ON)(ONC)+
V(ONCH2)+
V(OC2)+ / 496
468
449
429
418
391
383
369
356
340
327
307
285
281
261
240
221
213
195
167
154
136
95
91

Table 5SomeimportantIRspectraldata(cm­1)of(vn), (vn-100), (vn-200), (vn-300) and (vn-400).

Sample / IR spectral data (cm-1)
(vn) / 3600-3200 br ν (-OH); 1600-1400s ν(Ph); 962s ν(V=N); 560s ν(V-O)
(vn-100) / 3600-3200 br ν (-OH); 1600-1450s ν(Ph);980s ν(V=N); 562s ν(V-O)
(vn-200) / 1600-1400s ν(Ph); 990s ν(V=N); 530s ν(V-O)
(vn-300) / 1025s ν(V=O); 840s ν(coupled vibrations between V=O and V-O-V bonds); 520 s ν(V-O)
(vn-400) / 1025s ν(V=O); 860s ν(coupled vibrations between V=O and V-O-V bonds); 522 s ν(V-O)