| Identifier | 1 |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 7.87–7.65 (m, 2H, NH), 6.21–6.08 (m, 2H, H-6), 6.08–5.85 (m, 2 H, H-5), 2.52 (s, 4H, H-3), 1.87 (q, JH-H = 7.4 Hz, 4H, H-9), 1.51 (hd, JH-H, H-P = 7.1, 2.2 Hz, 4H, H-2), 1.06–0.85 (m, 24H, H-1), 0.77 (t, JH-H = 7.4 Hz, 6H, H-10) |
| ¹³C NMR (101 MHz, C₆D₆) | δ 135.6 (2 × C, C-7), 127.9 (2 × C, C-4), 106.6 (2 × CH, C-6), 106.4 (d, J = 4.4 Hz, 2 × CH, C-5), 43.7 (C, C-8), 29.4 (2 × CH2, C-9), 23.8 (d, JC-P = 14.7 Hz, 4 × CH, C-2), 21.4 (d, JC-P = 20.5 Hz, 2 × CH2, C-3), 20.0 (d, JC-P = 15.2 Hz, 4 × CH3, C-1), 18.7 (d, JC-P = 9.8 Hz, 4 × CH3, C-1), 8.5 (2 × CH3, C-10) |
| ¹H–¹³C HMBC, C-4 | Located at 127.9 ppm beneath the solvent signal; multiplicity could not be assigned |
| ³¹P NMR (162 MHz, C₆D₆) | δ 0.42 (s) |
| HRMS (ASAP-ESI, m/z) | Calc’d for C27H49N2P2 [M + H]⁺ 463.33655; found 463.3368 |
Sergio Fernandez, Ruogu Li, Carlos Martín-Fernández, Graham J. Tizzard, Simon J. Coles, Stuart A. Macgregor, Oriol Planas. “Dehydrogenative access to aluminyl metalloligands.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007508/v1
| Identifier | 2 |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 6.35 (bs, 4H, H-5 + H-6), 4.47 (bs, 2H, Al-H), 3.47 (bs, 2H, H-3), 3.13 (bs, 2H, H-3), 2.18 (bs, 4H, H-9), 1.59 (s, 4H, H-2), 0.93 (s, 30H, H-1 + H-10) |
| ¹³C NMR (101 MHz, C₆D₆) | δ 144.9 (2 × C-7), 111.9 (2 × CH, C-6), 106.3 (2 × CH, C-5), 48.5 (C, C-8), 41.8 (2 × CH2, C-9), 25.1–17.4 (m, 6 × CH2 + 4 × CH + 8 × CH3, C-12 + C-1 + C-2), 10.4 (2 × CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ −1.52 (q, JP-Li = 70.4, 68.5 Hz) |
| ⁷Li NMR (156 MHz, C₆D₆) | δ 1.87 (bs) |
| ²⁷Al NMR (104 MHz, C₆D₆) | δ 109.25 (bs) |
| HRMS (ASAP-ESI, m/z) | Calc’d for C24H41AlLi2N2P2 [M + Li]⁺ 503.3428; found 503.3441 |
| Identifier | 2-THF |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 6.47–6.11 (m, 4H, H-5 + H-6), 4.31 (bs, 2H, Al-H), 3.45–3.34 (m, 8H, H-11), 3.26 (bs, 4H, H-3), 2.22 (q, JH-H = 7.2 Hz, 4H, H-9), 1.88–1.57 (m, 4H, H-2), 1.42–1.22 (m, 8H, H-12), 1.18–0.79 (m, 30H, H-1 + H-10) |
| ¹³C NMR (101 MHz, C₆D₆) | δ 144.1 (2 × C, C-7), 130.0 (2 × C, C-4), 109.7 (2 × CH, C-6), 106.1 (2 × CH, C-5), 68.8 (4 × CH2, C-11), 47.4 (C, C-8), 38.4 (2 × CH2, C-9), 25.4 (4 × CH2, C-12), 23.8 (d, JC-P = 7.3 Hz, C-1, 2 × CH2, C-3), 23.2 (d, JC-P = 4.4 Hz, 4 × CH, C-2), 19.5 (d, JC-P = 8.8 Hz, 4 × CH3, C-1), 19.4 (d, JC-P = 8.8 Hz, 4 × CH3, C-1), 10.5 (2 × CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ −2.18 (s) |
| ⁷Li NMR (156 MHz, C₆D₆) | δ 0.04 (bs) |
| ²⁷Al NMR (104 MHz, C₆D₆) | δ 110.38 (bs) |
| HRMS (ASAP-HESI, m/z) | Calc’d for C35H64AlLi2N2O2P2 [M + Li]⁺ 647.4578; found 647.2318 |
| Identifier | 2-DMAP |
|---|---|
| NMR in THF-d₈ | A mixture of products |
| HRMS (ASAP-HESI, m/z) | Calc’d for C41H68AlLi2N6P2 [M + Li]⁺ 747.5116; found 747.5129 |
| Identifier | 3a |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 8.35 (d, JH-H = 7.5 Hz, 2H, H-11), 6.45 (d, JH-H = 2.9 Hz, 2H, H-6), 6.41 (d, JH-H = 3.1 Hz, 2H, H-5), 5.59 (d, JH-H = 7.5 Hz, 2H, H-12), 3.30–3.12 (m, 2H, H-2a), 3.11–2.97 (m, 2H, H-3b), 2.62 (d, JH-P = 13.9 Hz, 2H, H-3a), 2.38 (q, JH-H = 7.3 Hz, 2H, H-9a), 2.32 (q, JH-H = 7.2 Hz, 2H, H-9b), 2.20–2.10 (m, 2H, H-2b), 1.81 (bs, 6H, H-14), 1.58 (aq, J = 7.3 Hz, 6H, H-1a), 1.48 (aq, J = 7.2 Hz, 6H, H-1b), 1.17 (t, JH-H = 7.3 Hz, 3H, H-10a), 1.08 (aq, J = 7.2 Hz, 6H, H-1b′), 1.04–0.95 (m, 9H, H-1a′ + H-10b) |
| NOE and COSY | Phosphine-arm signals and the ethyl group of the backbone were assigned |
| ¹³C NMR (101 MHz, C₆D₆) | δ 155.5 (C-C13), 146.9 (2 × CH, C-11), 143.3 (2 × C, C-7), 127.4 (2 × C, C-4), 109.1 (2 × CH, C-5), 106.2 (4 × CH, C-6 + C-12), 48.2 (C, C-8), 42.3 (CH2, C-9), 41.5 (CH2, C-9), 38.2 (2 × CH3, C-14), 28.7 (at, JC-P = 11.0 Hz, 2 × CH, C-2), 24.0 (at, JC-P = 9.8 Hz, 2 × CH, C-2), 22.4 (at, JC-P = 12.0 Hz, 2 × CH, C-3), 21.2 (2 × CH3, C-1), 20.5 (2 × CH3, C-1), 20.2 (2 × CH3, C-1), 17.3 (2 × CH3, C-1), 11.5 (CH3, C-10), 10.5 (CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ 28.54 (s) |
| Reaction-mixture ³¹P{¹H} NMR | δP = 28.0 ppm for the major new species |
| HRMS (ASAP-HESI, m/z) | Calc’d for C34H56AlN4NiP2 [M − Cl]⁺ 667.3149; found 667.3155 |
| CHN | C34H56AlClN4NiP2 calcd. C 58.01, H 8.02, N 7.96 %; exp. C 58.17, H 8.09, N 8.17 % |
| Identifier | 3b |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 8.32 (d, JH-H = 6.8 Hz, 2H, H-11), 6.43 (d, JH-H = 2.8 Hz, 2H, H-6), 6.40 (d, JH-H = 3.1 Hz, 2H, H-5), 5.60 (d, JH-H = 7.0 Hz, 2H, H-12), 3.36–3.22 (m, 2H, H-2a), 3.15–3.03 (m, 2H, H-3b), 2.60 (d, JH-P = 14.5 Hz, 2H, H-3a), 2.37 (q, JH-H = 7.2 Hz, 2H, H-9a), 2.34–2.21 (m, 4H, H-2b + H-9b), 1.86 (bs, 6H, H-14), 1.57 (aq, J = 7.3 Hz, 6H, H-1a), 1.48 (aq, J = 7.2 Hz, 6H, H-1b), 1.17 (t, JH-H = 7.3 Hz, 3H, H-10a), 1.09–0.97 (m, 15H, H-1a′ + H-1b′ + H-10b) |
| ¹H NMR assignments | Phosphine-arm signals were assigned by analogy to species 3a |
| ¹³C NMR (101 MHz, C₆D₆) | δ 155.5 (C-C13), 146.8 (2 × CH, C-11), 143.4 (2 × C, C-7), 127.0 (2 × C, C-4), 109.1 (2 × CH, C-5), 106.2 (2 × CH, C-12), 106.2 (2 × CH, C-6), 48.1 (C, C-8), 42.4 (CH2, C-9), 41.3 (CH2, C-9), 38.5 (2 × CH3, C-14), 29.0 (at, JC-P = 11.2 Hz, 2 × CH, C-2), 25.7 (at, JC-P = 10.0 Hz, 2 × CH, C-2), 22.3 (at, JC-P = 11.7 Hz, 2 × CH, C-3), 21.3 (2 × CH3, C-1), 20.9 (2 × CH3, C-1), 20.0 (2 × CH3, C-1), 17.6 (2 × CH3, C-1), 11.5 (CH3, C-10), 10.5 (CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ 28.75 (s) |
| HRMS (ASAP-HESI, m/z) | Calc’d for C34H56AlN4NiP2 [M − Br]⁺ 667.3149; found 667.3168 |
| CHN | C34H56AlBrN4NiP2 calcd. C 54.57, H 7.54, N 7.49 %; exp. C 54.17, H 7.53, N 7.63 % |
| Identifier | 3c |
|---|---|
| ¹H NMR (400 MHz, THF-d₈) | δ 8.20 (d, JH-H = 7.5 Hz, 2H, H-11), 6.77 (d, JH-H = 7.5 Hz, 2H, H-12), 5.88 (d, JH-H = 3.2 Hz, 2H, H-6), 5.84 (d, JH-H = 2.9 Hz, 2H, H-5), 3.10 (s, 6H, H-14), 3.20–3.03 (m, 4H, H-2a + H-3b), 2.43 (d, JH-P = 14.4 Hz, 2H), 2.36–2.25 (m, 2H, H-3a), 1.93 (aq, JH-H = 7.2 Hz, 3H, H-9a), 1.87 (aq, JH-H = 7.2 Hz, 3H, H-9b), 1.39 (aq, JH-H = 7.2 Hz, 6H, H-1a), 1.20 (aq, JH-H = 7.2 Hz, 6H, H-1b), 1.12 (aq, J = 7.0 Hz, 6H, H-1b′), 0.89 (aq, J = 7.0 Hz, 6H, H-1b), 0.70 (t, JH-H = 7.3 Hz, 2H, H-10a), 0.48 (t, JH-H = 7.2 Hz, 2H, H-10b) |
| ¹H NMR assignments | Phosphine-arm signals were assigned by analogy to species 3a |
| ¹³C NMR (101 MHz, THF-d₈) | δ 157.6 (C-C13), 147.4 (2 × CH, C-11), 143.5 (2 × C, C-7), 128.1 (2 × C, C-4), 108.9 (2 × CH, C-5), 107.7 (2 × CH, C-12), 106.0 (2 × CH, C-6), 48.4 (C, C-8), 42.6 (CH2, C-9), 41.8 (CH2, C-9), 39.5 (2 × CH3, C-14), 30.1 (at, JC-P = 11.2 Hz, 2 × CH, C-2), 29.2 (at, JC-P = 10.0 Hz, 2 × CH, C-2), 22.0 (at, JC-P = 11.7 Hz, 2 × CH, C-3), 21.7 (2 × CH3, C-1), 21.6 (2 × CH3, C-1), 19.7 (2 × CH3, C-1), 18.6 (2 × CH3, C-1), 11.5 (CH3, C-10), 10.5 (CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ 29.21 (s) |
| HRMS (ASAP-HESI, m/z) | Calc’d for C34H56AlN4NiP2 [M − I]⁺ 667.3149; found 667.3111 |
| CHN | C34H56AlIN4NiP2 calcd. C 51.34, H 7.10, N 7.04 %; exp. C 51.21, H 7.21, N 7.07 % |
| Identifier | 4 |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 8.27 (d, JH-H = 7.5 Hz, 2H, H-11), 6.43 (d, JH-H = 3.1 Hz, 2H, H-6), 6.40 (d, JH-H = 3.1 Hz, 2H, H-5), 5.61 (d, JH-H = 7.5 Hz, 2H, H-12), 3.30–3.14 (m, 2H, H-2a), 3.13–3.03 (m, 2H, H-3b), 2.67 (d, JH-P = 14.8 Hz, 2H, H-3a), 2.38 (q, JH-H = 7.2 Hz, 2H, H-9a), 2.29 (q, JH-H = 7.1 Hz, 2H, H-9b), 2.10–2.01 (m, 2H, H-2b), 1.84 (bs, 6H, H-14), 1.56 (aq, J = 7.2 Hz, 6H, H-1a), 1.45 (aq, J = 7.2 Hz, 6H, H-1b), 1.16 (t, JH-H = 7.2 Hz, 3H, H-10a), 1.08–0.86 (m, 15H, H-1a' H-1b’ + H10b) |
| ¹H NMR assignments | Phosphine-arm signals were assigned by analogy to species 3a |
| ¹³C NMR (101 MHz, C₆D₆) | δ 155.7 (C, C-13), 147.0 (2 × CH, C-11), 143.7 (2 × C, C-7), 127.9 (2 × C, C-4), 109.9 (2 × CH, C-5), 106.3 (2 × C-H, C-12), 106.2 (2 × CH, C-6), 48.5 (C, C-8), 42.4 (CH2, C-9), 42.0 (CH2, C-9), 38.3 (2 × CH3, C-14), 28.5 (at, JC-P = 11.5 Hz, 2 × CH, C-2), 24.3 (at, JC-P = 11.0 Hz, 2 × CH, C-2), 22.1 (at, JC-P = 9.5 Hz, 2 × CH2, C-3), 21.0 (2 × CH3, C-1), 20.3 (4 × CH3, C-1), 17.0 (2 × CH3, C-1), 11.5 (CH3, C-10), 10.3 (CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ 31.25 (s) |
| Stability at room temperature | Full decomposition after 16 h both in solid state and in solution to a bright red oil or a pink solution, respectively |
| Identifier | 5 |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 8.43 (d, JH-H = 7.3 Hz, 2H, H-11), 6.43 (d, JH-H = 3.0 Hz, 2H, H-6), 6.42–6.35 (m, 2H, H-5), 5.58 (d, JH-H = 7.4 Hz, 2H, H-12), 3.64–3.13 (m, 4H, H-2a + H-3b), 2.78 (d, JH-P = 14.7 Hz, 2H, H-3a), 2.47–2.21 (m, 6H, H-2b + H-9a), 1.80 (bs, 6H, H-14), 1.56 (aq, J = 7.3 Hz, 6H, H-1a), 1.45 (aq, J = 7.2 Hz, 6H, H-1b), 1.20 (t, JH-H = 7.3 Hz, 3H, H-10a), 1.08–0.90 (m, 15H, H-1a’ + H1-b’ + H-10b) |
| ¹H NMR assignments | Phosphine-arm signals were assigned by analogy to species 3a |
| ¹³C NMR (101 MHz, C₆D₆) | δ 155.6 (C, C-13), 147.2 (2 × CH, C-11), 143.9 (2 × C, C-7), 127.1 (2 × C, C-4), 110.0 (2 × CH, H-5), 106.2 (2 × CH, H-12), 106.0 (2 × CH, C-5), 48.3 (C, C-8), 43.1 (CH2, C-9), 39.6 (CH2, C-9), 38.2 (2 × CH3, C-14), 29.0 (at, JC-P = 11.5 Hz, 2 × CH, C-2), 23.7 (at, JC-P = 11.5 Hz, 2 × CH, C-2), 22.7 (at, JC-P = 11.5 Hz, 2 × CH, C-3), 20.3 (2 × CH3, C-1), 19.9 (2 × CH3, C-1), 19.5 (2 × CH3, C-1), 17.0 (2 × CH3, C-1), 11.4 (CH3, C-10), 10.3 (CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ 39.71 (s), 39.71 (d, JP-Pt = 2860.1 Hz) |
| ²⁷Al NMR (104 MHz, C₆D₆) | δ −1.32 (bs) |
| HRMS (ASAP-HESI, m/z) | Calc’d for C34H56AlN4P2Pt [M − Cl]⁺ 804.3444; found 804.3442 |
| CHN | C34H56AlClN4P2Pt calcd. C 48.60, H 6.72, N 6.67 %; exp. C 48.77, H 6.31, N 6.88 % |
| Identifier | 8 |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 6.28 (d, JH-H = 2.7 Hz, 2Hz, H-6), 6.23–6.18 (m, 2H, H-5), 3.54 (s, 3H, H-11), 2.94 (d, JH-P = 14.2 Hz, 2H, H-3a), 2.60–2.47 (m, 2H, H-3b), 2.51 (q, JH-H = 7.1 Hz, 2H, H-9a), 2.33 (q, JH-H = 7.1 Hz, 2H, H-9b), 1.45–1.31 (m, 6H, H-2), 1.19 (t, JH-H = 7.1 Hz, 3H, H-10a), 1.11 (t, JH-H = 7.3 Hz, 3H, H-10b), 0.94–0.84 (m, 12H, H-1a + H-1b), 0.66 (aq, J = 7.1 Hz, 12H, H-1a’ + H-1b’), −28.84 (t, JH-P = 70.5 Hz, 1H, Ni-H) |
| ¹³C NMR (101 MHz, C₆D₆) | δ 145.8 (2 × C, C-7), 125.5 (2 × C, C-4), 110.7 (2 × CH, H-5), 108.1 (2 × CH, H-12), 53.8 (CH3, C-11), 46.8 (C, C-8), 40.5 (CH2, C-9), 29.3 (CH2, C-9), 25.6–24.9 (m, 4 × CH2, C-2), 22.1 (at, JC-P = 11.5 Hz, 2 × CH2, C-3), 19.0 (d, JC-P = 12.2 Hz, 4 × CH3, C-1), 17.9 (d, JC-P = 12.2 Hz, 4 × CH3, C-1), 10.6 (CH3, C-10a), 10.0 (CH3, C-10b) |
| ³¹P NMR (162 MHz, C₆D₆) | δ 41.22–39.48 (m, 2P) |
| Solid-state stability at room temperature | Compound 8 is also unstable in solid state, evolving at room temperature to the formation of multiple different Ni-H species |
| Identifier | 7 |
|---|---|
| ¹H NMR (500 MHz, THF-d₈) | δ 5.56 (d, JH-H = 2.8 Hz, 4H, H-6), 5.49 (d, JH-H = 2.7 Hz, 4H, H-5), 3.13 (d, JH-P = 13.8 Hz, 4H, H-3b), 3.02 (d, JH-P = 13.6 Hz, 4H, H-3a), 2.30 (q, JH-H = 7.3 Hz, 4H, H-9a), 2.10–1.94 (m, 4H, H-2a), 2.03 (q, JH-H = 7.3 Hz, 4H, H-9b), 1.65 (hept, J = 7.2 Hz, 4H, H-2b), 1.20–0.95 (m, 42H, H-1a + H-1a’ + H-1b + H-10b), 0.67 (t, JH-H = 7.3 Hz, 6H, H-10a), 0.51–0.40 (m, 12H, H-1b’), −4.57 (s, 2H, H-11) |
| ¹³C NMR (126 MHz, THF-d₈) | δ 144.4 (4 × C, C-7), 131.6 (4 × C, C-4), 106.8 (4 × CH, C-5), 104.2 (4 × CH, C-6), 46.4 (2 × C, C-8), 37.1 (2 × CH2, C-9a), 30.5–30.3 (m, 4 × CH, C-2a), 30.3–29.9 (m, 4 × CH2, C-3) 27.5 (2 × CH2, C-9b), 27.4 (bs, 4 × CH, C-2b), 20.3 (4 × CH3, C-1b), 20.0 (8 × CH3, C-1a + C-1a’), 19.2 (4 × CH3, C-1b’), 11.4 (2 × CH3, C-10b), 10.3 (2 × CH3, C-10a) |
| ³¹P NMR (202 MHz, THF-d₈) | δ 37.2 |
| HRMS (ASAP-HESI, m/z) | Calc’d for C54H94Al2LiN4Ni2P4 [M + Li]⁺ 1099.4927; found 1099.4827 |
| CHN | C42H66Al2N4Ni2P2 calcd. C 58.64, H 7.73, N 6.51 %; exp. C 58.77, H 7.77, N 6.58 % |
| Identifier | 6 |
|---|---|
| ¹H NMR (400 MHz, C₆D₆) | δ 6.49 (d, JH-H = 3.3 Hz, 2H, H-6), 6.47 (d, JH-H = 3.2 Hz, 2H, H-5), 2.85–2.64 (m, 4H, H-3), 2.33 (q, JH-H = 7.2 Hz, 4H, H-9), 1.61–1.42 (m, 4H, H-2), 1.21 (t, JH-H = 7.3 Hz, 6H, H-10), 1.03–0.85 (m, 12H, H-1), 0.85–0.72 (m, 12H, H-1) |
| ¹³C NMR (101 MHz, C₆D₆) | δ 138.9 (2 × C, C-7), 131.9 (at, JC-P = 4.2 Hz, 2 × C, C-4), 105.9 (2 × CH, C-6), 103.1 (at, JC-P = 6.0, Hz 2 × CH, C-5), 48.1 (C, C-8), 38.5 (2 × CH2, C-9), 24.9 (at, JC-P = 10.0 Hz, 4 × CH, C-2), 22.5 (at, JC-P = 14.2 Hz, 2 × CH2, C-3), 20.4 (4 × CH3, C-1), 18.3 (4 × CH3, C-1), 10.6 (2 × CH3, C-10) |
| ³¹P NMR (162 MHz, C₆D₆) | δ 63.16 (s) |
| CHN | C27H46N2NiP2 calcd. C 62.45, H 8.93, N 5.39 %; exp. C 62.52, H 8.97, N 5.38 % |
| Identifier | 2-DMAP |
|---|---|
| Aluminium geometry, τ4 | 0.93 |
| Al–N distances | 1.865(1) and 1.8704(9) Å |
| Al–H distances | 1.60(1) and 1.61(1) Å |
| Hydride positions | Located in the Fourier difference map and refined using a riding model |
| Al–Li separation | 2.989(2) Å |
| Disordered P(iPr)2 moiety | Approximately 86:14 |
| Empirical formula | C₄₁H₆₈AlLiN₆P₂ |
| Calculated density | 1.109 g cm⁻³ |
| μ | 0.152 mm⁻¹ |
| Formula weight | 740.906 |
| Crystal colour | Colourless |
| Crystal shape | Block-shaped |
| Crystal size | 0.10 × 0.09 × 0.07 mm |
| Temperature | 100(2) K |
| Crystal system | Triclinic |
| Space group | P-1 |
| a | 11.6787(1) Å |
| b | 11.6979(1) Å |
| c | 17.1681(2) Å |
| α | 97.235(1)° |
| β | 91.338(1)° |
| γ | 107.083(1)° |
| Volume | 2219.60(4) ų |
| Z | 2 |
| Z′ | 1 |
| Wavelength | 0.71073 Å |
| Radiation type | Mo Kα |
| θ range | 1.83–33.73° |
| Index ranges | −18 ≥ h ≥ 18, −18 ≥ k ≥ 18, −18 ≥ l ≥ 26 |
| Measured reflections | 126873 |
| Independent reflections | 17739 |
| Reflections I≥2σ(I) | 12878 |
| Rint | 0.0465 |
| Parameters | 547 |
| Restraints | 115 |
| Largest peak / deepest hole | 1.0781 / −0.5451 e Å⁻³ |
| GooF | 1.0250 |
| R1 [I≥2σ(I) / all] | 0.0480 / 0.0744 |
| wR2 [I≥2σ(I) / all] | 0.1176 / 0.1310 |
| Identifier | 3a |
|---|---|
| Aluminium geometry, τ4 | 0.84 |
| Al–Ni distance | 2.2697(6) Å |
| Nickel geometry, τ4 | 0.11 |
| P–Ni–P angle | 169.33(2)° |
| Whole-molecule disorder | Approximately 82:18 |
| Empirical formula | C₃₄H₅₆AlClN₄NiP₂ |
| Calculated density | 1.293 g cm⁻³ |
| μ | 0.753 mm⁻¹ |
| Formula weight | 703.925 |
| Crystal colour | Yellow |
| Crystal shape | Block-shaped |
| Crystal size | 0.08 × 0.07 × 0.03 mm |
| Temperature | 100(2) K |
| Crystal system | Triclinic |
| Space group | P-1 |
| a | 13.4932(1) Å |
| b | 17.9125(2) Å |
| c | 18.0621(2) Å |
| α | 117.072(1)° |
| β | 108.648(1)° |
| γ | 90.936(1)° |
| Volume | 3614.75(8) ų |
| Z | 4 |
| Z′ | 2 |
| Wavelength | 0.71073 Å |
| Radiation type | Mo Kα |
| θ range | 1.62–38.12° |
| Index ranges | −23 ≥ h ≥ 22, −30 ≥ k ≥ 27, −30 ≥ l ≥ 31 |
| Measured reflections | 167596 |
| Independent reflections | 36875 |
| Reflections I≥2σ(I) | 29337 |
| Rint | 0.0390 |
| Parameters | 1574 |
| Restraints | 1806 |
| Largest peak / deepest hole | 0.7473 / −0.8455 e Å⁻³ |
| GooF | 1.0568 |
| R1 [I≥2σ(I) / all] | 0.0458 / 0.0645 |
| wR2 [I≥2σ(I) / all] | 0.1011 / 0.1084 |
| Identifier | 4 |
|---|---|
| Palladium geometry, τ4 | 0.13 |
| Aluminium geometry, τ4 | 0.83 |
| Al–Pd distance | 2.3513(3) Å |
| Empirical formula | C₃₄H₅₆AlClN₄P₂Pd |
| Calculated density | 1.385 g cm⁻³ |
| μ | 0.732 mm⁻¹ |
| Formula weight | 751.648 |
| Crystal colour | Colourless |
| Crystal shape | Block-shaped |
| Crystal size | 0.15 × 0.10 × 0.09 mm |
| Temperature | 100(2) K |
| Crystal system | Triclinic |
| Space group | P-1 |
| a | 12.4833(2) Å |
| b | 12.9172(2) Å |
| c | 13.7228(2) Å |
| α | 83.644(1)° |
| β | 66.996(1)° |
| γ | 62.618(1)° |
| Volume | 1802.16(5) ų |
| Z | 2 |
| Z′ | 1 |
| Wavelength | 0.71073 Å |
| Radiation type | Mo Kα |
| θ range | 1.62–38.11° |
| Index ranges | −19 ≥ h ≥ 21, −21 ≥ k ≥ 22, 0 ≥ l ≥ 23 |
| Measured reflections | 86463 |
| Independent reflections | 18573 |
| Reflections I≥2σ(I) | 16771 |
| Rint | 0.0304 |
| Parameters | 400 |
| Restraints | 0 |
| Largest peak / deepest hole | 1.0848 / −0.4771 e Å⁻³ |
| GooF | 1.0456 |
| R1 [I≥2σ(I) / all] | 0.0211 / 0.0262 |
| wR2 [I≥2σ(I) / all] | 0.0446 / 0.0462 |
| Identifier | 5 |
|---|---|
| Platinum geometry, τ4 | 0.08 |
| Aluminium geometry, τ4 | 0.84 |
| Al–Pt distance | 2.3306(3) Å |
| Empirical formula | C₃₄H₅₆AlClN₄P₂Pt |
| Calculated density | 1.538 g cm⁻³ |
| μ | 4.066 mm⁻¹ |
| Formula weight | 840.310 |
| Crystal colour | Colourless |
| Crystal shape | Block-shaped |
| Crystal size | 0.21 × 0.17 × 0.14 mm |
| Temperature | 100(2) K |
| Crystal system | Monoclinic |
| Space group | P21/m |
| a | 11.0292(3) Å |
| b | 14.6017(3) Å |
| c | 12.1300(2) Å |
| α | 90° |
| β | 111.723(2)° |
| γ | 90° |
| Volume | 1814.75(7) ų |
| Z | 2 |
| Z′ | 0.5 |
| Wavelength | 0.71073 Å |
| Radiation type | Mo Kα |
| θ range | 1.81–38.03° |
| Index ranges | −18 ≥ h ≥ 17, 0 ≥ k ≥ 25, 0 ≥ l ≥ 20 |
| Measured reflections | 46447 |
| Independent reflections | 9641 |
| Reflections I≥2σ(I) | 8678 |
| Rint | 0.0350 |
| Parameters | 257 |
| Restraints | 0 |
| Largest peak / deepest hole | 1.8592 / −0.8766 e Å⁻³ |
| GooF | 1.0317 |
| R1 [I≥2σ(I) / all] | 0.0244 / 0.0314 |
| wR2 [I≥2σ(I) / all] | 0.0498 / 0.0519 |
| Identifier | 7 |
|---|---|
| Core | Centrosymmetric Al2Ni2H2 |
| Al–N distances | 1.848(2) and 1.851(2) Å |
| Ni–P distances | 2.2367(7) and 2.2703(7) Å |
| Al–Ni distances | 2.3285(8) and 2.4244(8) Å |
| Ni···Ni separation | 2.6380(4) Å |
| Hydride position | Located in the difference map and freely refined |
| Ni–H distance | 1.66(2) Å |
| Al–H distance | 1.68(2) Å |
| Ni–H–Al angle | 93(1)° |
| Empirical formula | C₅₄H₉₄Al₂N₄Ni₂P₄ |
| Calculated density | 1.317 g cm⁻³ |
| μ | 0.869 mm⁻¹ |
| Formula weight | 1094.620 |
| Crystal colour | Colourless |
| Crystal shape | Block-shaped |
| Crystal size | 0.04 × 0.01 × 0.01 mm |
| Temperature | 100(2) K |
| Crystal system | Monoclinic |
| Space group | P21/n |
| a | 12.9518(5) Å |
| b | 13.3978(5) Å |
| c | 15.9258(6) Å |
| α | 90° |
| β | 92.491(3)° |
| γ | 90° |
| Volume | 2760.92(18) ų |
| Z | 2 |
| Z′ | 0.5 |
| Wavelength | 0.71073 Å |
| Radiation type | Mo Kα |
| θ range | 1.98–28.28° |
| Index ranges | −17 ≥ h ≥ 13, 0 ≥ k ≥ 17, −12 ≥ l ≥ 21 |
| Measured reflections | 64232 |
| Independent reflections | 6852 |
| Reflections I≥2σ(I) | 4704 |
| Rint | 0.1155 |
| Parameters | 440 |
| Restraints | 0 |
| Largest peak / deepest hole | 0.8403 / −0.7092 e Å⁻³ |
| GooF | 1.0421 |
| R1 [I≥2σ(I) / all] | 0.0431 / 0.0838 |
| wR2 [I≥2σ(I) / all] | 0.0779 / 0.0902 |
| Identifier | 8 |
|---|---|
| Mixed Ni hydride/chloride model | Approximately 80:20 |
| Disordered ethyl group | Approximately 85:15 |
| Empirical formula | C₃₁H₅₆.₈AlCl₁.₂N₂NiOP₂ |
| Calculated density | 1.299 g cm⁻³ |
| μ | 0.812 mm⁻¹ |
| Formula weight | 663.689 |
| Crystal colour | Red |
| Crystal shape | Lath-shaped |
| Crystal size | 0.10 × 0.04 × 0.02 mm |
| Temperature | 100(2) K |
| Crystal system | Monoclinic |
| Space group | P21/n |
| a | 9.2857(2) Å |
| b | 15.5190(3) Å |
| c | 23.7166(4) Å |
| α | 90° |
| β | 96.702(2)° |
| γ | 90° |
| Volume | 3394.32(11) ų |
| Z | 4 |
| Z′ | 1 |
| Wavelength | 0.71073 Å |
| Radiation type | Mo Kα |
| θ range | 1.57–36.14° |
| Index ranges | −15 ≤ h ≤ 15, −25 ≤ k ≤ 25, −38 ≤ l ≤ 38 |
| Measured reflections | 140193 |
| Independent reflections | 15365 |
| Reflections I≥2σ(I) | 11573 |
| Rint | 0.0595 |
| Parameters | 389 |
| Restraints | 5 |
| Largest peak / deepest hole | 1.0986 / −0.7416 e Å⁻³ |
| GooF | 1.0298 |
| R1 [I≥2σ(I) / all] | 0.0381 / 0.0642 |
| wR2 [I≥2σ(I) / all] | 0.0753 / 0.0831 |