Nitrile coordination to rhodium does not lead to C—H activation

Tris(pyrazol­yl)borate complexes of rhodium are well known to activate C—H bonds. The reactive [Tp′Rh(PMe₃)] fragment [Tp′ is tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borate] is found to react with valero­nitrile to give the κ¹N-bound com­plex (penta­nenitrile-κN)(tri­methyl­phosphane-κP)[tris­(3,5-di­methyl­imid­a­zol-1-yl)hydro­borato-κ²N²,N^2′]rhodium(I), [Rh(C₁₅H₂₂BN₆)(C₅H₉N)(C₃H₉P)]. In con­trast to the widespread evidence for the reaction of this fragment with C—H bonds via oxidative addition, no evidence for such a complex is observed.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

(Pentanenitrile-κN)(trimethylphosphane-κP)[tris(3,5-dimethylimidazol-1-yl)hydroborato-κ²N²,N^2']rhodium(I)

Crystal data

[Rh(C15H22BN6)(C5H9N)(C3H9P)]	F(000) = 584
Mr = 559.31	Dx = 1.377 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 8.4544 (8) Å	Cell parameters from 4074 reflections
b = 15.0084 (14) Å	θ = 2.4–27.9°
c = 10.6904 (10) Å	µ = 0.72 mm^−1
β = 95.975 (2)°	T = 100 K
V = 1349.1 (2) Å^3	Needle, yellow
Z = 2	0.18 × 0.16 × 0.10 mm

Data collection

Bruker SMART APEXII CCD Platform diffractometer	12861 independent reflections
Radiation source: fine-focus sealed tube	9022 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
ω scans	θmax = 36.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −14→14
Tmin = 0.697, Tmax = 0.747	k = −24→24
36418 measured reflections	l = −17→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0278P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
12861 reflections	Δρmax = 1.25 e Å^−3
313 parameters	Δρmin = −1.02 e Å^−3
1 restraint	Absolute structure: Refined as an inversion twin.
Primary atom site location: difference Fourier map	Absolute structure parameter: 0.05 (3)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component racemic twin (95:05).

The borohydride hydrogen atom was found from the difference Fourier map and refined freely.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rh1	0.54121 (3)	0.29151 (2)	0.19412 (3)	0.01279 (6)
P1	0.62592 (10)	0.29078 (15)	0.39694 (8)	0.01597 (18)
N1	0.3661 (4)	0.3823 (3)	0.2105 (3)	0.0152 (7)
N2	0.2113 (4)	0.3587 (3)	0.1738 (3)	0.0134 (7)
N3	0.4300 (4)	0.2737 (2)	0.0110 (3)	0.0146 (9)
N4	0.2686 (4)	0.2579 (2)	−0.0015 (3)	0.0133 (7)
N5	0.1479 (4)	0.2047 (3)	0.3221 (3)	0.0171 (7)
N6	0.2036 (4)	0.1921 (3)	0.2080 (3)	0.0135 (7)
B1	0.1715 (5)	0.2677 (3)	0.1112 (4)	0.0136 (9)
H1	0.045 (5)	0.270 (3)	0.077 (4)	0.014 (12)*
C1	0.3653 (5)	0.4672 (3)	0.2464 (4)	0.0179 (9)
C2	0.2099 (6)	0.4993 (3)	0.2365 (4)	0.0179 (9)
H2	0.1760	0.5572	0.2579	0.021*
C3	0.1149 (5)	0.4291 (3)	0.1891 (4)	0.0164 (8)
C4	0.4788 (5)	0.2620 (3)	−0.1021 (4)	0.0150 (8)
C5	0.3501 (5)	0.2392 (3)	−0.1891 (4)	0.0163 (8)
H5	0.3525	0.2271	−0.2761	0.020*
C6	0.2198 (5)	0.2378 (3)	−0.1228 (4)	0.0153 (8)
C7	0.1777 (5)	0.1299 (3)	0.3865 (4)	0.0170 (9)
C8	0.2532 (5)	0.0677 (3)	0.3156 (4)	0.0188 (9)
H8	0.2868	0.0093	0.3402	0.023*
C9	0.2687 (5)	0.1092 (3)	0.2019 (4)	0.0161 (8)
C10	0.5160 (6)	0.5158 (3)	0.2847 (5)	0.0237 (10)
H10A	0.6065	0.4757	0.2788	0.036*
H10B	0.5161	0.5366	0.3716	0.036*
H10C	0.5247	0.5670	0.2289	0.036*
C11	−0.0614 (5)	0.4267 (3)	0.1542 (5)	0.0226 (10)
H11A	−0.1055	0.3730	0.1894	0.034*
H11B	−0.0839	0.4260	0.0624	0.034*
H11C	−0.1100	0.4796	0.1880	0.034*
C12	0.6488 (5)	0.2760 (3)	−0.1241 (4)	0.0194 (12)
H12A	0.7093	0.2959	−0.0459	0.029*
H12B	0.6551	0.3213	−0.1894	0.029*
H12C	0.6935	0.2199	−0.1514	0.029*
C13	0.0498 (5)	0.2184 (3)	−0.1673 (4)	0.0216 (10)
H13A	0.0111	0.1702	−0.1169	0.032*
H13B	0.0412	0.2005	−0.2559	0.032*
H13C	−0.0143	0.2720	−0.1584	0.032*
C14	0.1313 (6)	0.1221 (4)	0.5176 (4)	0.0253 (11)
H14A	0.0804	0.1776	0.5406	0.038*
H14B	0.2263	0.1112	0.5762	0.038*
H14C	0.0567	0.0725	0.5217	0.038*
C15	0.3348 (5)	0.0712 (3)	0.0891 (4)	0.0184 (9)
H15A	0.2545	0.0749	0.0162	0.028*
H15B	0.3638	0.0087	0.1050	0.028*
H15C	0.4293	0.1050	0.0720	0.028*
N7	0.7006 (4)	0.2004 (3)	0.1645 (3)	0.0155 (7)
C16	0.7795 (5)	0.1432 (3)	0.1411 (4)	0.0174 (9)
C17	0.8701 (5)	0.0629 (3)	0.1141 (4)	0.0203 (9)
H17A	0.9657	0.0581	0.1756	0.024*
H17B	0.9056	0.0676	0.0290	0.024*
C18	0.7669 (6)	−0.0202 (3)	0.1216 (5)	0.0228 (10)
H18A	0.6748	−0.0162	0.0566	0.027*
H18B	0.8297	−0.0733	0.1028	0.027*
C19	0.7058 (6)	−0.0326 (3)	0.2501 (4)	0.0217 (10)
H19A	0.6263	−0.0812	0.2442	0.026*
H19B	0.6514	0.0227	0.2723	0.026*
C20	0.8370 (6)	−0.0544 (4)	0.3549 (5)	0.0321 (13)
H20A	0.7913	−0.0582	0.4353	0.048*
H20B	0.9180	−0.0075	0.3596	0.048*
H20C	0.8858	−0.1116	0.3370	0.048*
C21	0.6523 (7)	0.1787 (3)	0.4612 (4)	0.0265 (11)
H21B	0.6829	0.1822	0.5521	0.040*
H21C	0.7359	0.1480	0.4209	0.040*
H21D	0.5524	0.1456	0.4453	0.040*
C22	0.8158 (6)	0.3405 (4)	0.4571 (5)	0.0265 (11)
H22A	0.8322	0.3331	0.5486	0.040*
H22D	0.8149	0.4041	0.4363	0.040*
H22B	0.9021	0.3110	0.4186	0.040*
C23	0.4891 (6)	0.3367 (4)	0.5005 (5)	0.0264 (11)
H23D	0.5265	0.3221	0.5879	0.040*
H23A	0.3830	0.3113	0.4789	0.040*
H23B	0.4842	0.4016	0.4905	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01127 (11)	0.01270 (12)	0.01410 (11)	0.0004 (2)	−0.00014 (8)	−0.0007 (2)
P1	0.0157 (4)	0.0171 (4)	0.0146 (4)	−0.0007 (9)	−0.0008 (3)	−0.0004 (9)
N1	0.0128 (16)	0.0155 (19)	0.0172 (17)	0.0002 (14)	0.0007 (13)	−0.0003 (14)
N2	0.0102 (16)	0.0153 (19)	0.0152 (17)	0.0005 (14)	0.0032 (13)	−0.0014 (14)
N3	0.0117 (14)	0.016 (3)	0.0159 (15)	0.0010 (12)	0.0004 (11)	−0.0009 (12)
N4	0.0099 (15)	0.0144 (16)	0.0154 (16)	−0.0023 (12)	0.0008 (12)	−0.0001 (12)
N5	0.0174 (18)	0.0188 (19)	0.0152 (17)	−0.0001 (15)	0.0023 (14)	0.0000 (14)
N6	0.0145 (17)	0.0137 (19)	0.0127 (17)	−0.0021 (15)	0.0031 (13)	−0.0004 (14)
B1	0.0112 (19)	0.013 (2)	0.017 (2)	−0.0015 (15)	0.0028 (16)	−0.0012 (15)
C1	0.021 (2)	0.014 (2)	0.018 (2)	−0.0005 (17)	0.0000 (17)	−0.0005 (16)
C2	0.020 (2)	0.010 (2)	0.024 (2)	0.0044 (17)	0.0045 (18)	0.0004 (17)
C3	0.015 (2)	0.016 (2)	0.018 (2)	0.0033 (17)	0.0034 (16)	0.0023 (16)
C4	0.0121 (18)	0.0151 (19)	0.0175 (19)	−0.0002 (14)	0.0003 (15)	0.0018 (14)
C5	0.016 (2)	0.018 (2)	0.0146 (19)	−0.0006 (17)	0.0012 (15)	−0.0008 (16)
C6	0.018 (2)	0.013 (2)	0.0141 (18)	−0.0020 (16)	−0.0016 (15)	−0.0007 (15)
C7	0.016 (2)	0.019 (2)	0.0153 (19)	−0.0017 (17)	0.0000 (15)	0.0024 (16)
C8	0.017 (2)	0.017 (2)	0.022 (2)	−0.0006 (17)	−0.0013 (17)	0.0047 (18)
C9	0.013 (2)	0.012 (2)	0.022 (2)	−0.0027 (16)	−0.0017 (17)	−0.0010 (17)
C10	0.022 (2)	0.015 (2)	0.033 (3)	−0.0024 (18)	−0.001 (2)	−0.0050 (19)
C11	0.014 (2)	0.022 (2)	0.032 (3)	0.0043 (18)	0.0029 (18)	0.002 (2)
C12	0.0152 (17)	0.023 (4)	0.0200 (18)	−0.0018 (17)	0.0027 (14)	0.0004 (17)
C13	0.017 (2)	0.031 (3)	0.016 (2)	−0.0037 (19)	−0.0017 (16)	−0.0051 (19)
C14	0.029 (3)	0.029 (3)	0.017 (2)	−0.001 (2)	0.0012 (19)	0.0035 (19)
C15	0.020 (2)	0.012 (2)	0.024 (2)	0.0011 (17)	0.0057 (17)	−0.0025 (17)
N7	0.0137 (17)	0.0175 (19)	0.0150 (17)	0.0001 (14)	0.0004 (13)	0.0028 (14)
C16	0.016 (2)	0.017 (2)	0.019 (2)	−0.0025 (17)	0.0005 (16)	0.0009 (16)
C17	0.017 (2)	0.019 (2)	0.025 (2)	0.0032 (18)	0.0050 (18)	−0.0032 (18)
C18	0.027 (2)	0.012 (2)	0.029 (2)	0.0010 (18)	0.0007 (19)	−0.0048 (18)
C19	0.020 (2)	0.016 (2)	0.029 (2)	−0.0069 (18)	0.0005 (18)	0.0001 (18)
C20	0.027 (3)	0.036 (3)	0.032 (3)	−0.009 (2)	−0.002 (2)	0.008 (2)
C21	0.036 (3)	0.021 (2)	0.021 (2)	−0.001 (2)	−0.002 (2)	0.0041 (19)
C22	0.022 (2)	0.033 (3)	0.022 (2)	−0.005 (2)	−0.0056 (19)	−0.002 (2)
C23	0.025 (2)	0.032 (3)	0.023 (2)	0.005 (2)	0.0068 (19)	0.000 (2)

Geometric parameters (Å, º)

Rh1—N1	2.033 (4)	C10—H10C	0.9800
Rh1—N7	1.968 (4)	C11—H11A	0.9800
Rh1—N3	2.098 (3)	C11—H11B	0.9800
Rh1—P1	2.2116 (9)	C11—H11C	0.9800
N7—C16	1.131 (6)	C12—H12A	0.9800
P1—C23	1.818 (5)	C12—H12B	0.9800
P1—C21	1.822 (5)	C12—H12C	0.9800
P1—C22	1.825 (5)	C13—H13A	0.9800
N1—C1	1.330 (6)	C13—H13B	0.9800
N1—N2	1.373 (5)	C13—H13C	0.9800
N2—C3	1.355 (6)	C14—H14A	0.9800
N2—B1	1.543 (6)	C14—H14B	0.9800
N3—C4	1.329 (5)	C14—H14C	0.9800
N3—N4	1.377 (5)	C15—H15A	0.9800
N4—C6	1.354 (5)	C15—H15B	0.9800
N4—B1	1.534 (6)	C15—H15C	0.9800
N5—C7	1.328 (6)	C16—C17	1.472 (7)
N5—N6	1.365 (5)	C17—C18	1.530 (7)
N6—C9	1.366 (6)	C17—H17A	0.9900
N6—B1	1.540 (6)	C17—H17B	0.9900
B1—H1	1.10 (4)	C18—C19	1.527 (7)
C1—C2	1.392 (6)	C18—H18A	0.9900
C1—C10	1.488 (6)	C18—H18B	0.9900
C2—C3	1.388 (6)	C19—C20	1.528 (6)
C2—H2	0.9500	C19—H19A	0.9900
C3—C11	1.499 (6)	C19—H19B	0.9900
C4—C5	1.399 (6)	C20—H20A	0.9800
C4—C12	1.495 (6)	C20—H20B	0.9800
C5—C6	1.371 (6)	C20—H20C	0.9800
C5—H5	0.9500	C21—H21B	0.9800
C6—C13	1.495 (6)	C21—H21C	0.9800
C7—C8	1.397 (6)	C21—H21D	0.9800
C7—C14	1.499 (6)	C22—H22A	0.9800
C8—C9	1.384 (6)	C22—H22D	0.9800
C8—H8	0.9500	C22—H22B	0.9800
C9—C15	1.494 (6)	C23—H23D	0.9800
C10—H10A	0.9800	C23—H23A	0.9800
C10—H10B	0.9800	C23—H23B	0.9800
N7—Rh1—N1	175.08 (15)	H11A—C11—H11C	109.5
N7—Rh1—N3	90.55 (14)	H11B—C11—H11C	109.5
N1—Rh1—N3	84.61 (13)	C4—C12—H12A	109.5
N7—Rh1—P1	89.83 (11)	C4—C12—H12B	109.5
N1—Rh1—P1	94.77 (11)	H12A—C12—H12B	109.5
N3—Rh1—P1	169.05 (10)	C4—C12—H12C	109.5
C23—P1—C21	100.5 (2)	H12A—C12—H12C	109.5
C23—P1—C22	102.8 (2)	H12B—C12—H12C	109.5
C21—P1—C22	100.1 (2)	C6—C13—H13A	109.5
C23—P1—Rh1	115.69 (17)	C6—C13—H13B	109.5
C21—P1—Rh1	112.88 (18)	H13A—C13—H13B	109.5
C22—P1—Rh1	121.76 (17)	C6—C13—H13C	109.5
C1—N1—N2	107.2 (4)	H13A—C13—H13C	109.5
C1—N1—Rh1	133.8 (3)	H13B—C13—H13C	109.5
N2—N1—Rh1	118.9 (3)	C7—C14—H14A	109.5
C3—N2—N1	109.4 (4)	C7—C14—H14B	109.5
C3—N2—B1	129.5 (4)	H14A—C14—H14B	109.5
N1—N2—B1	120.7 (4)	C7—C14—H14C	109.5
C4—N3—N4	106.7 (3)	H14A—C14—H14C	109.5
C4—N3—Rh1	135.5 (3)	H14B—C14—H14C	109.5
N4—N3—Rh1	117.1 (2)	C9—C15—H15A	109.5
C6—N4—N3	109.3 (3)	C9—C15—H15B	109.5
C6—N4—B1	129.8 (3)	H15A—C15—H15B	109.5
N3—N4—B1	120.9 (3)	C9—C15—H15C	109.5
C7—N5—N6	106.4 (4)	H15A—C15—H15C	109.5
N5—N6—C9	110.3 (4)	H15B—C15—H15C	109.5
N5—N6—B1	116.4 (4)	C16—N7—Rh1	172.8 (4)
C9—N6—B1	133.1 (4)	N7—C16—C17	174.4 (5)
N4—B1—N6	112.7 (3)	C16—C17—C18	110.2 (4)
N4—B1—N2	108.4 (3)	C16—C17—H17A	109.6
N6—B1—N2	110.2 (3)	C18—C17—H17A	109.6
N4—B1—H1	109 (2)	C16—C17—H17B	109.6
N6—B1—H1	110 (2)	C18—C17—H17B	109.6
N2—B1—H1	106 (2)	H17A—C17—H17B	108.1
N1—C1—C2	110.0 (4)	C19—C18—C17	113.2 (4)
N1—C1—C10	121.2 (4)	C19—C18—H18A	108.9
C2—C1—C10	128.7 (4)	C17—C18—H18A	108.9
C3—C2—C1	105.7 (4)	C19—C18—H18B	108.9
C3—C2—H2	127.1	C17—C18—H18B	108.9
C1—C2—H2	127.1	H18A—C18—H18B	107.7
N2—C3—C2	107.6 (4)	C18—C19—C20	113.4 (4)
N2—C3—C11	123.1 (4)	C18—C19—H19A	108.9
C2—C3—C11	129.2 (4)	C20—C19—H19A	108.9
N3—C4—C5	110.1 (4)	C18—C19—H19B	108.9
N3—C4—C12	121.3 (4)	C20—C19—H19B	108.9
C5—C4—C12	128.6 (4)	H19A—C19—H19B	107.7
C6—C5—C4	105.7 (4)	C19—C20—H20A	109.5
C6—C5—H5	127.1	C19—C20—H20B	109.5
C4—C5—H5	127.1	H20A—C20—H20B	109.5
N4—C6—C5	108.1 (4)	C19—C20—H20C	109.5
N4—C6—C13	122.4 (4)	H20A—C20—H20C	109.5
C5—C6—C13	129.5 (4)	H20B—C20—H20C	109.5
N5—C7—C8	110.8 (4)	P1—C21—H21B	109.5
N5—C7—C14	119.8 (4)	P1—C21—H21C	109.5
C8—C7—C14	129.4 (4)	H21B—C21—H21C	109.5
C9—C8—C7	105.5 (4)	P1—C21—H21D	109.5
C9—C8—H8	127.3	H21B—C21—H21D	109.5
C7—C8—H8	127.3	H21C—C21—H21D	109.5
N6—C9—C8	107.0 (4)	P1—C22—H22A	109.5
N6—C9—C15	125.0 (4)	P1—C22—H22D	109.5
C8—C9—C15	127.9 (4)	H22A—C22—H22D	109.5
C1—C10—H10A	109.5	P1—C22—H22B	109.5
C1—C10—H10B	109.5	H22A—C22—H22B	109.5
H10A—C10—H10B	109.5	H22D—C22—H22B	109.5
C1—C10—H10C	109.5	P1—C23—H23D	109.5
H10A—C10—H10C	109.5	P1—C23—H23A	109.5
H10B—C10—H10C	109.5	H23D—C23—H23A	109.5
C3—C11—H11A	109.5	P1—C23—H23B	109.5
C3—C11—H11B	109.5	H23D—C23—H23B	109.5
H11A—C11—H11B	109.5	H23A—C23—H23B	109.5
C3—C11—H11C	109.5
C1—N1—N2—C3	−0.9 (5)	B1—N2—C3—C2	−172.6 (4)
Rh1—N1—N2—C3	−178.3 (3)	N1—N2—C3—C11	178.2 (4)
C1—N1—N2—B1	172.5 (4)	B1—N2—C3—C11	5.5 (7)
Rh1—N1—N2—B1	−4.9 (5)	C1—C2—C3—N2	0.9 (5)
C4—N3—N4—C6	−0.8 (4)	C1—C2—C3—C11	−177.1 (5)
Rh1—N3—N4—C6	−172.9 (3)	N4—N3—C4—C5	0.4 (5)
C4—N3—N4—B1	−178.5 (3)	Rh1—N3—C4—C5	170.3 (3)
Rh1—N3—N4—B1	9.5 (5)	N4—N3—C4—C12	178.5 (4)
C7—N5—N6—C9	−0.2 (5)	Rh1—N3—C4—C12	−11.6 (6)
C7—N5—N6—B1	175.6 (4)	N3—C4—C5—C6	0.1 (5)
C6—N4—B1—N6	110.4 (5)	C12—C4—C5—C6	−177.8 (4)
N3—N4—B1—N6	−72.5 (5)	N3—N4—C6—C5	0.9 (5)
C6—N4—B1—N2	−127.3 (4)	B1—N4—C6—C5	178.3 (4)
N3—N4—B1—N2	49.8 (5)	N3—N4—C6—C13	−179.0 (4)
N5—N6—B1—N4	167.2 (3)	B1—N4—C6—C13	−1.6 (7)
C9—N6—B1—N4	−18.3 (6)	C4—C5—C6—N4	−0.6 (5)
N5—N6—B1—N2	46.0 (5)	C4—C5—C6—C13	179.3 (5)
C9—N6—B1—N2	−139.5 (5)	N6—N5—C7—C8	0.0 (5)
C3—N2—B1—N4	118.3 (5)	N6—N5—C7—C14	179.7 (4)
N1—N2—B1—N4	−53.6 (5)	N5—C7—C8—C9	0.1 (5)
C3—N2—B1—N6	−118.0 (5)	C14—C7—C8—C9	−179.5 (4)
N1—N2—B1—N6	70.1 (5)	N5—N6—C9—C8	0.2 (5)
N2—N1—C1—C2	1.5 (5)	B1—N6—C9—C8	−174.5 (4)
Rh1—N1—C1—C2	178.3 (3)	N5—N6—C9—C15	177.2 (4)
N2—N1—C1—C10	−176.2 (4)	B1—N6—C9—C15	2.4 (8)
Rh1—N1—C1—C10	0.6 (7)	C7—C8—C9—N6	−0.2 (5)
N1—C1—C2—C3	−1.4 (5)	C7—C8—C9—C15	−177.0 (4)
C10—C1—C2—C3	176.0 (5)	C16—C17—C18—C19	−59.0 (5)
N1—N2—C3—C2	0.0 (5)	C17—C18—C19—C20	−67.9 (5)