6212 Inorganic Chemistry, Vol. 49, No. 13, 2010
Spasyuk and Zargarian
in 20 mL of benzene was slowly added to the stirring suspension
of NiBr2(CH3CN)x (0.503 g, 1.66 mmol) and triethylamine
(0.230 mL, 1.66 mmol) in toluene (5 mL) at r. t. The resulting
dark brown mixture was then heated for 3 h at 60 °C, washed with
water (3 ꢀ 5 mL), and evaporated to dryness to give the crude
product as an oily yellow powder (0.656 g, 93%). Chromatogra-
phy through a short pad of silica gel (eluents: hexane followed by
50:50 CH2Cl2/Hexane) gave an analytically pure sample (0.553 g,
78%).
1H NMR (δ, C6D6): 1.17 (dd, 3JHP = 14, 3JHH = 7, 6H, 2 ꢀ
3
3
CHCH3), 1.54 (dd, JHP = 18, JHH = 7, 6H, 2 ꢀ CHCH3),
2.21-2.34 (m, 2H, PCH), 3.73 (s, 2H, ArCH2), 4.08 (dd, 2JHH
=
13, 2JHP = 3, 2H, {Bn}CH2), 5.09 (d, 2JHH = 13, 2H, {Bn}CH2),
6.34 (d, 3JHH = 7, 1H, {Ar}H5), 6.58 (d, 3JHH = 8, 1H, {Ar}H3),
3
6.83 (t, JHH = 8, 1H, {Ar}H4), 7.13-7.07 (m, 6H, 4 ꢀ
{Bn}Hmetha, 2 ꢀ {Bn}Hpara), 7.75-7.67 (m, 4H, 4 ꢀ {Bn}Hortho).
13C{1H} NMR (δ, C6D6): 16.81 (s, 2C, 2 ꢀ CHCH3), 18.18 (d,
2JCP = 4, 2C, 2 ꢀ CHCH3), 28.42 (d, 1JCP = 25, 2C, 2 ꢀ PCH),
58.91 (s, 1C, ArCH2), 59.49 (s, 2C, 2 ꢀ BnCH2), 108.26 (d,
1H NMR (δ, C6D6): 1.19 (dd, JHP = 14, JHH = 7, 3H,
CHCH3) 1.25 (dd, JHP = 15, JHH = 7, 3H, CHCH3), 1.50 (dd,
JHP/HH = 7, 3H, CHCH3), 1.54 (dd, JHP/HH =6, 3H, CHCH3),
2.33-2.11 (m, 2H, 2 ꢀ PCH), 3.22 (br. s, 1H, NH), 3.33 (dd,
2
3JCP = 13, 1C, {Ar}C3), 115.94 (d, JCP = 2, 1C, {Ar}C5),
127.15 (s, 1C, {Ar}C4), 128.42 (s, 4C, 4 ꢀ {Bn}Cmetha), 128.45 (s,
2C, 2 ꢀ {Bn}Cpara), 132.04 (s, 4C, 4 ꢀ {Bn}Cortho), 134.32 (s, 2C,
{Bn}Cipso), 142.60 (d, 2JCP = 34, 1C, {Ar}C1Ni), 151.56 (s, 1C,
{Ar}C6), 165.80 (d, 2JCP = 10, 1C, {Ar}C2) 31P{1H} NMR (δ,
C6D6): 200.87 (s, 1P).
3
2
2JHH = 16, JHH = 6, 1H, ArCH2N), 3.42 (dd, JHH =16,
3JHH = 4, 1H, ArCH2N), 3.83 (dd, 2JHH = 14, 3JHH = 10, 1H,
{Bn}CH2), 4.63 (d, 2JHH = 14, 1H, {Bn}CH2), 6.32 (d, 3JHH
7, 1H, {Ar}H5), 6.62 (d, 3JHH = 8, 1H, {Ar}H3), 6.86 (t, 3JHH
=
=
Anal. Calcd for C27H33OPNNiBr: C, 58.21, H, 5.97; N, 2.51;
Found: C, 58.24; H, 6.03; N, 2.49.
8, 1H, {Ar}H4), 7.04 (m, 3H, 2 ꢀ {Bn}Hmeta, {Bn}Hpara), 7.11
(d, 3JHH = 5, 2H, 2 ꢀ {Bn}Hortho). 13C{1H} NMR (δ, C6D6):
[KP,KC,KN-{2,6-(i-Pr2PO)(C6H3)(CH2NBn)}Ni]2 (5). To a
stirred solution of 1 (0.500 g, 1.07 mmol) in dry and degassed
toluene (10 mL) at -78 °C was added MeLi as a solution (0.393
mL of a 3 M solution in diethoxymethane, 1.18 mmol) or a solid
(26 mg, 1.18 mmol), and the resulting red mixture was stirred for
30 min, allowed to warm to r.t., and stirred for additional 32 h at
60 °C (or stirred for 1 week at room temperature). Conversion of
1 to 5 was monitored by 31P{1H} NMR spectroscopy. At the end
of reaction, the mixture was washed with water (10 mL ꢀ 3) and
evaporated under reduced pressure to give an orange powder
(0.367 g, 89%).
2
16.61 (d, JCP = 2, 1C, CH3), 17.14 (s, 1C, CH3), 18.17 (d,
2JCP = 4, 2C, 2 ꢀ CH3), 28.36 (d, 1JCP = 10, 2C, CH), 28.60 (d,
1JCP = 9, 1C, CH), 54.27 (s, 1C, CH2), 57.62 (s, 1C, CH2), 108.27
(d, 3JCP = 13, 1C, {Ar}C3), 115.59 (s, 1C, {Ar}C5), 127.10 (s, 1C,
{Ar}C4), 128.55 (s, 1C, {Bn}Cpara), 128.83 (s, 2C, 2 ꢀ
{Bn}Cortho), 129.25 (s, 2C, 2 ꢀ {Bn}Cmeta), 137.22 (s, 1C,
2
{Bn}Cipso), 143.46 (d, JCP = 32, 1C, {Ar}C1Ni), 152.75 (s,
1C, {Ar}C6), 166.16 (d, 2JCP = 10, 1C, {Ar}C2). 31P{1H} NMR
(δ, C6D6): 201.72 (s,1P).
Anal. Calcd for C20H27OPNNiBr: C, 51.44; H, 5.73; N, 3.00;
Found: C, 51.28; H, 5.83; N, 2.90.
1H NMR (δ, C6D6): 1.12-0.91 (m, 12H, 4 ꢀ CHCH3), 1.23
(dd, 3JHP = 17, 3JHH=7, 6H, 2 ꢀ CHCH3), 1.71 (dd, 3JHP = 16,
3JHH = 7, 6H, 2 ꢀ CHCH3), 2.13-1.86 (m, 4H, 4 ꢀ PCH), 3.58
(dd, 2JHH = 17, JHP = 10 2H, BnCH2), 3.97 (d, 2JHH = 18, 2H,
ArCH2), 4.16 (d, 2JHH = 18, 2H, ArCH2), 4.55 (d, 2JHH = 17,
KP,KC,KN-{2-(i-Pr2PO)(6-(CH2N(Bn)(allyl)(C6H3))}NiBr (3).
To a stirred solution of 1 (0.100 g, 0.216 mmol) in a dry and
degassed 1:1 mixture of hexane: THF or dry and degassed
toluene (5 mL) at -78 °C was added a MeLi solution in dietho-
xymethane (0.108 mL, 3 M, 0.323 mmol), and the resulting red
mixture stirred for 30 min. Allyl bromide (0.042 mL, 0.485 mmol)
was then added, and the mixture stirred for one more hour
at -78 °C, and then overnight at r.t. Complex 3 was isolated
by flash chromatography (SiO2, benzene) as a yellow powder
(0.071 g, 64%).
3
2H, BnCH2), 6.49 (d, JHH = 7, 2H, 2 ꢀ {Ar}H5), 6.67 (d,
3JHH = 8, 2H, 2 ꢀ {Ar}H3), 6.92 (t, 3JHH = 8, 2H, 2 ꢀ {Ar}H4),
3
7.06 (t, JHH = 7, 2H, 2 ꢀ {Bn}Hpara), 7.17 (m, 4H, 4 ꢀ
3
{Bn}Hmeta, overlapping with C6D5H) 7.77 (d, JHH = 7, 4H,
4 ꢀ {Bn}Hortho). 13C{1H} NMR (δ, C6D6): 15.08 (d, 2JCP = 6,
2C, 2 ꢀ CHCH3), 16.60 (d, 2JCP = 9, 2C, 2 ꢀ CHCH3), 18.57 (s,
2C, 2 ꢀ CHCH3), 19.04 (s, 2C, 2 ꢀ CHCH3), 28.97 (d, 1JCP
=
1H NMR (δ, C6D6): 1.17 (2 ꢀ dd, 3JHP = 15, 3JHH = 7, 6H,
2 ꢀ CHCH3), 1.48 (dd, 3JHP = 11, 3JHH = 7, 3H, CHCH3), 1.53
(dd, 3JHP = 11, 3JHH = 7, 3H, CHCH3), 2.24 (m, 2H, 2 ꢀ PCH),
24, 2C, 2 ꢀ PCH), 29.15 (d, 1JCP = 17, 2C, 2 ꢀ PCH,), 59.28 (s,
2C, 2 ꢀ BnCH2), 72.42 (s, 2C, 2 ꢀ ArCH2), 106.75 (d, 3JCP = 13,
2C, 2 ꢀ {Ar}C3), 114.20 (s, 2C, 2 ꢀ {Ar}C5), 126.09 (s, 2C, 2 ꢀ
{Ar}C6), 126.28 (s, 2C, 2 ꢀ {Bn}Cpara), 126.94 (s, 4C, 4 ꢀ
{Bn}Cortho), 128.14 (s, 4C, 4 ꢀ {Bn}Cmeta, found by DEPT),
2.87 (ddd, JHH = 12, 9, JHP2= 4, 1H, CH2CH), 3.65 (d, 2JHH
=
16, 1H, ArCH2), 3.81 (d, JHH = 16, 1H, ArCH2), 4.03 (dd,
2
2JHH = 13, JHP = 2, 1H, CH2{Bn}), 4.33 (dd, JHH = 13,
2
142.51 (s, 2C, 2 ꢀ {Bn}Cipso), 145.80 (d, JCP = 30, 2C, 2 ꢀ
2
3JHH = 5, 1H, CH2CH), 4.84 (d, JHH = 13, 1H, CH2{Bn}),
{Ar}C1Ni), 158.31 (s, 2C, 2 ꢀ {Ar}C6), 165.78 (d, 2JCP = 11, 2C,
4.96 (d, 3JHH = 17, 1H, trans-CH2=), 5.04 (d, 3JHH = 10, 1H,
cis-CH2=), 6.37 (d, 3JHH = 8, 1H, {Ar}H5), 6.58 (d, 3JHH = 8,
1H, {Ar}H3), 6.84 (t, 3JHH = 8, 1H, {Ar}H4), 6.83-6,92 (m, 1H,
CH2CH), 7.13-7.02 (m, 3H, 2 ꢀ {Bn}Hortho, {Bn}Hpara), 7.58
(d, 3JHH = 6, 2H, {Bn}Hmeta). 13C{1H} NMR (δ, C6D6): 16.88
2 ꢀ {Ar}C2). 31P{1H} NMR (δ, C6D6): 191.6 (s, 2P).
Anal. Calcd for C40H52O2P2N2Ni2: C, 62.22, H, 6.97; N, 3.63;
Found: C, 62.37; H, 6.94; N, 3.48.
General Procedure for the Reactivity Survey. An NMR tube
was charged with a C6D6 solution of 5 (10.0 mg, 0.013 mmol, in
0.6 mL) and the desired amount of the reagent to be studied as
follows: m-toluidine: 4.5 μL, 0.065 mmol; m-cresol: 10 μL of a
0.0013 M solution in C6D6 in the first step, followed by 9.5 μL of
neat m-cresol, 0.091 mmol; 2,6-dimethyl(phenyl)isonitrile:
8.5 mg, 0.065 mmol; phthalimide: 9.5 mg, 0.065 mmol;
CO: excess; TFE 7.5 μL, 0.104 mmol; N-hydroxyphthalimide:
10.6 mg, 0.065 mmol. The NMR tube was capped with a rubber
septum and placed in an oil bath at 50 °C for a predetermined
period of time. The progress of the reactions was monitored by
NMR spectroscopy.
2
2
(d, JCP = 22, 2C, 2 ꢀ CHCH3), 18.19 (d, JCP = 4 Hz, 1C,
CHCH3), 18.24 (d, 2JCP = 4 Hz, 1C, CHCH3), 28.37 (d, 1JCP
=
25 Hz, 1C, PCH), 28.68 (d, 1JCP = 25 Hz, 1C, PCH), 61.07 (s,
1C, ArCH2N), 61.20 (s, 1C, BnCH2), 61.80 (s, 1C, AllylCH2),
108.16 (d, 2JCP = 13 Hz, 1C, {Ar}C3), 115.41 (s, 1C, {Ar}C5),
120.48 (s, 1C, CH2dCH), 127.09 (s, 1C, {Ar}C4), 128.25 (s, 1C,
{Bn}Cpara found by DEPT), 128.43 (s, 2C, 2 ꢀ {Bn}Cmeta),
131.99 (s, 2C, 2 ꢀ {Bn}Cortho), 133.98 (s, 1C, CH2=CH), 134.03
2
(s, 1C, {Bn}Cipso), 142.53 (d, JCP = 33 Hz, 1C, {Ar}C1Ni),
152.21 (s, 1C, {Ar}C6), 165.73 (d, 2JCP = 11 Hz, 1C, {Ar}C2).
31P{1H} NMR (δ, C6D6): 200.64 (s, 1P).
Anal. Calcd for C23H31OPNNiBr: C, 54.48, H, 6.16; N, 2.76;
Found: C, 54.70; H, 6.23; N, 2.73.
KP,KC,KN-{2,6-(i-Pr2PO)(C6H3)(CH2NBn2)}NiBr (4). The
procedure described above for the preparation of 3 was used
to prepare this complex, which was isolated as a yellow powder
(0.068 g, 57%).
Typical Procedure Used for Catalytic Hydroalkoxylation of
Acrylonitrile. The catalytic runs were conducted in air. The
reaction vessel was charged with acrylonitrile (e.g., 0.100 g,
1.887 mmol), the alcohol (e.g., 0.810 g, 18.87 mmol of EtOH),
and dodecane as the internal standard (0.046 g, 0.269 mmol).
The catalyst precursor 5 was then added (1.00 mL of a 0.0094 M