NCH2N); 3.93-3.80 (m, 2H, PCH2N), 3.74 (dd, J = 15
and 8 Hz, 1H, PCH2N), 2.71-2.81 (m, 1H, P-CH-C),
2.35-2.44 (m, 1H, P-CH-C), 1.24-1.36 (m, 12H, C-CH3).
13C{1H} NMR (100 MHz, CDCl3): δ 74.4 (dd, JPC = 1
um. The resulting brown-yellow solid was dissolved
in CH2Cl2 and filtered through a plug of silica gel.
Methanol was added to the CH2Cl2 and the solution
cooled to 0 ºC resulting in the precipitation of 5 as a
yellow crystalline solid (0.090 g, 32 % yield). 1H NMR
3
and 8 Hz, NCH2N), 71.4 (d, JPC = 10 Hz, NCH2N),
67.7 (d, 3JPC = 10 Hz, NCH2N), 59.6 (dd, 1JPC = 55 and
37 Hz, PCHP), 56.4 (dd, JPC = 51 and 5 Hz, PCH2N),
(400 MHz, CD2Cl2): δ 4.95 (t, JPH = 12 Hz, 1H,
2
PCHP), 4.63 (d, J = 13 Hz, 6H, NCH2N), 4.56-4.42 (m,
1H, PCH2N), 4.42-4.31 (m, 1H, PCH2N), 4.26 (ddd, J =
15, 10, and 5 Hz, 2H, PCH2N); 4.09, 3.96 (AB quartet,
J = 15 Hz, 2H, PCH2N); 2.55 (dtd, J = 14, 7, and 3 Hz,
1H, PCHC), 2.40 (qd, J = 14 and 7 Hz, 1H, PCHC),
1
53.0 (d, JPC = 52 Hz, PCH2N), 27.9 (dd, J = 59 and 9
Hz, PCHC), 25.6 (dd, JPC = 61 and 3 Hz, PCHC), 16.2
2
(dd, JPC = 18 and 2 Hz, CCH3), 15.4 (d, JPC = 7 Hz,
2
CCH3), 15.04 (s, CCH3), 15.01 (d, JPC = 1 Hz, CCH3).
2
31P{1H} NMR (162 MHz, CDCl3): δ 57.04 (d, JPP = 5
1.44-1.32 (m, 6H, CCH3), 1.28-1.15 (m, 6H, CCH3).
=
2
2
Hz, O=PiPr2), -8.85 (d, JPP = 5 Hz, O=PTA). IR νPO
13C{1H} NMR (100 MHz, CD2Cl2): δ 209.3 (dd, JPC
(CH2Cl2, cm-1): 1185.5 (m), 1174.0 (m). X-ray-quality
crystals were obtained by slow evaporation of a 1:5
CH2Cl2:hexanes solution resulting in the formation
of clear colorless blocks over the course of 2 days.
24 and 7 Hz, trans-CO), 208.8 (dd, JPC = 25 and 7
Hz, trans-CO), 204.0 (t, 2JPC = 8 Hz, cis-CO), 201.6 (t,
2JPC = 6 Hz, cis-CO), 77.0 (t, 3JPC = 5 Hz, NCH2N) 74.9
(dd, 1JPC = 22, and 10 Hz, PCHP), 73.4 (d, 3JPC = 6 Hz,
2
NCH2N), 69.8 (d, 3JPC = 8 Hz, NCH2N), 55.9 (d, 1JPC
=
Synthesis
of
6-(CH2)2(NiPr)2P-1,3,5-triaza-7-
15 Hz, PCH2N), 54.9 (d, 1JPC = 9 Hz, PCH2N), 29.8 (d,
phosphaadamantane
dioxide, O=PTA-
1
1JPC = 14 Hz, PCHC), 24.2 (dd, JPC = 13 and 7 Hz,
OP(NiPr)2(CH2)2 (4): PTA-P(NiPr)2(CH2)2 (2) (0.100
mg, 0.304 mmol) was dissolved in CH2Cl2 followed
by the addition of three drops of 30 % H2O2. The re-
action was immediately opened to air and the solvent
evaporated with a draft of nitrogen. The resulting
colorless solid (0.987 g, 90 % yield) was character-
2
2
PCHC), 22.7 (d, JPC = 8 Hz, CCH3), 21.0 (d, JPC = 7
Hz, CCH3), 20.1 (s, CCH3), 19.5 (d, 2JPC = 7 Hz, CCH3).
2
31P{1H} NMR (162 MHz, CD2Cl2): δ 52.7 (d, Jpp = 19
Hz, 1JPW = 190 Hz, PiPr2), -91.7 (d, 2JPP = 19 Hz, 1JPW
=
188 Hz, PTA). IR νCO (CH2Cl2, cm-1): 2012 (m), 1906
(sh), 1891 (vs), 1876 (sh). HRMS (ESI, CH3CN) m/z
calc. for C16H26N3O4P2W: [M+H]+ 565.0787; found
565.0800. Crystals suitable for X-ray diffraction were
obtained by slow evaporation of dichloromethane
solution, resulting in light yellow blocks after a few
days.
1
ized without further purification. H NMR (400
MHz, CDCl3): 4.64-4.50 (m, 1H, NCH2N), 4.39 (dd, J
= 24 and 13 Hz, 2H, NCH2N), 4.11 (ddt, J = 19, 13, and
4 Hz, 3H, NCH2N, NCHC), 4.09, 5.24 (AB quartet, J =
14 Hz, 2H, NCH2N), 3.91 (dd, J = 18 and 14 Hz, 1H,
PCHP), 3.85-3.75 (m, 2H, PCH2N), 3.64 (td, J = 13 and
7 Hz, 2H, NCHC, PCH2N), 3.32 – 3.19 (m, 2H,
NCH2C), 3.11-2.97 (m, 2H, NCH2C), 1.19 (dd, J = 7 and
3 Hz, 6H, CCH3), 1.12 (dd, J = 15 and 7 Hz, 6H, CCH3).
13C{1H} NMR (100 MHz, CDCl3): δ 75.4 (dd, JPC = 12
and 7 Hz, NCH2N), 72.7 (d, 3JPC = 9 Hz, NCH2N), 69.1
(d, 1JPC = 38 Hz, P-C-P), 67.9 (dd, JPC = 24 and 13 Hz,
NCH2N), 57.5 (d, JPC = 7 Hz, NCH2N), 57.0 (d, 2JPC = 7
Synthesis of [W(CO)4(PTA-P(NiPr)2(CH2)2] (6):
PTA-P(NiPr)2(CH2)2 (2) (0.035 g, 0.106 mmol) and
cis-[W(CO)4(NHC5H10)2] (0.050 g, 0.107 mmol) were
dissolved in 10 mL degassed dichloromethane and
stirred for two days at room temperature. The solvent
was removed and the resulting yellow solid dissolved
in 3 mL dichloromethane and filtered through celite.
Addition of 80 mL hexanes and placement in a freez-
er for 3 hours resulted in a precipitate. Filtration and
subsequent drying in vacuo resulted in an 89 % yield
1
Hz, PCH2N), 53.4 (d, JPC = 53 Hz, PCH2N), 45.1 (d,
2JPC = 5 Hz, NCHC), 44.3 (d, 2JPC = 5 Hz, NCHC), 37.7
(dd, J = 12 and 3 Hz, NCH2CH2N), 21.6 (d, 3JPC = 7 Hz,
CCH3), 21.5 (s, CCH3) 21.2 (d, 3JPC = 4 Hz, CCH3), 21.0
1
of 6 as a yellow solid (0.598 g). H NMR (400 MHz,
31
(s, CCH3). P{1H} NMR (162 MHz, CDCl3): δ 24.89
CDCl3): δ 5.10, 4.38 (AB quartet, J = 13 Hz, 2H,
NCH2N); 4.67, 4.38 (AB quartet, J = 13 Hz, 2H,
NCH2N); 4.56-4.45 (m, 2H, NCH2N), 4.42-4.33 (m,
3H, PCHP; PCH2N), 4.14-4.01 (m, 3H, NCHC; NCHC;
PCH2N), 3.95 (apparent doublet, J = 14 Hz, 1H,
PCH2N), 3.50 (tdd, J = 10, 7, and 3 Hz, 1H,
NCH2CH2N), 3.20-2.97 (m, 3H, NCH2CH2N), 1.30 (d,
JHH = 7 Hz, 3H, CCH3), 1.25 (d, JHH = 7 Hz, 3H, CCH3),
1.21 (d, JHH = 7 Hz, 3H, CCH3), 1.09 (d, JHH = 7 Hz, 3H,
CCH3). 13C{1H} NMR (100 MHz, CDCl3): δ 208.9-
208.4 (m, trans-CO), 208.3-207.8 (m, trans-CO),
(bs, PR2), -10.53 (bs, PTA). IR νPO (CH2Cl2, cm-1):
1185.6(m) and 1169.8(m). X-ray quality crystals were
obtained by slow evaporation of a 1:1 solution of
CH2Cl2:hexanes resulting in the formation of clear
and colorless plates over the course of 4 days.
Synthesis of [W(CO)4(PTA-PiPr2)] (5): PTA-PiPr2
(1) (0.137 g, 0.5 mmol) was added to a degassed di-
chloromethane solution of cis-[W(CO)4(NHC5H10)2]
(232 mg, 0.5 mmol). The solution was refluxed for
two hours and the solvent was removed under vacu-
2
2
204.8 (t, JPC = 7 Hz, cis-CO), 203.0 (t, JPC = 6 Hz,