1-tert-Butyl-2-methyl­phospho­lane-borane and its coupling product 2,2'-bis(1-tert-butyl­phospho­lane-borane)

The title compound, C₉H₂₂BP, and its coupling product, C₁₆H₃₈B₂P₂, were synthesized and their crystal structures analyzed by X-ray diffraction. The molecular structures clearly explain the stereoselective reaction pathways leading to the products. The average P-B distance and C-P-B angle are 1.929 Å and 114°, respectively.

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

(II)

Crystal data

C9H22BP	Melting point = 301–303 K
Mr = 172.06	Cu Kα radiation, λ = 1.5418 Å
Orthorhombic, Pna21	Cell parameters from 25 reflections
a = 12.52 (2) Å	θ = 7.3–34.7°
b = 6.944 (1) Å	µ = 1.69 mm^−1
c = 12.919 (1) Å	T = 123 K
V = 1123 (1) Å^3	Prismatic, colorless
Z = 4	0.40 × 0.30 × 0.30 mm
Dx = 1.017 Mg m^−3

Data collection

Rigaku AFC7S diffractometer	Rint = 0.02
ω–2θ scans	θmax = 67.6°
Absorption correction: ψ scan (North et al., 1968)	h = −15→0
Tmin = 0.576, Tmax = 0.602	k = 0→8
1056 measured reflections	l = 0→15
1056 independent reflections	3 standard reflections every 150 reflections
1030 reflections with F^2 > 2.0σ(F^2)	intensity decay: 1.0%

Refinement

Refinement on F	w = 1/[σ^2(Fo) + 0.00022|Fo|^2]
R[F^2 > 2σ(F^2)] = 0.039	(Δ/σ)max = 0.012
wR(F^2) = 0.050	Δρmax = 0.40 e Å^−3
S = 1.91	Δρmin = −0.34 e Å^−3
1030 reflections	Extinction correction: Zachariasen (1967) type 2 Gaussian isotropic
102 parameters	Extinction coefficient: 0.035 (7)
H-atom parameters not refined

Special details

Refinement. Refinement using reflections with F² > 2.0 σ(F²). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
P	0.81816 (4)	0.17946 (7)	0.0538 (7)	0.0193 (1)
C1	0.9571 (2)	0.1250 (3)	0.0168 (7)	0.0217 (5)
C2	0.9652 (2)	0.2016 (4)	−0.0945 (7)	0.0291 (6)
C3	0.9051 (2)	0.3912 (4)	−0.0990 (6)	0.0342 (6)
C4	0.7956 (2)	0.3588 (4)	−0.0476 (7)	0.0297 (6)
C5	0.8211 (2)	0.2990 (3)	0.1818 (7)	0.0248 (6)
C6	0.8719 (2)	0.1596 (4)	0.2585 (7)	0.0350 (7)
C7	0.7054 (2)	0.3439 (4)	0.2137 (7)	0.0342 (7)
C8	0.8852 (2)	0.4881 (4)	0.1793 (7)	0.0355 (7)
C9	0.9882 (2)	−0.0858 (3)	0.0285 (7)	0.0321 (6)
B	0.7184 (2)	−0.0311 (4)	0.0452 (7)	0.0313 (6)
H1	1.0034	0.1994	0.0587	0.0255*
H2	0.9355	0.1106	−0.1423	0.0364*
H3	1.0396	0.2187	−0.1130	0.0364*
H4	0.8973	0.4326	−0.1699	0.0414*
H5	0.9448	0.4893	−0.0633	0.0414*
H6	0.7677	0.4773	−0.0186	0.0370*
H7	0.7437	0.3137	−0.0970	0.0370*
H8	0.9444	0.1305	0.2343	0.0449*
H9	0.8768	0.2139	0.3245	0.0449*
H10	0.8337	0.0423	0.2600	0.0449*
H11	0.6659	0.2303	0.2146	0.0423*
H12	0.7059	0.4041	0.2793	0.0423*
H13	0.6751	0.4321	0.1639	0.0423*
H14	0.8874	0.5472	0.2446	0.0434*
H15	0.8572	0.5762	0.1292	0.0434*
H16	0.9585	0.4595	0.1583	0.0434*
H17	0.6473	0.0129	0.0524	0.0404*
H18	0.7258	−0.0961	−0.0197	0.0404*
H19	0.7326	−0.1237	0.0993	0.0404*
H20	0.9807	−0.1255	0.0988	0.0400*
H21	1.0602	−0.1057	0.0073	0.0400*
H22	0.9427	−0.1654	−0.0135	0.0400*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0193 (3)	0.0217 (3)	0.0169 (3)	−0.0019 (2)	0.0007 (3)	−0.0007 (3)
C1	0.0205 (9)	0.0217 (9)	0.023 (1)	−0.0036 (8)	0.0017 (9)	−0.0020 (9)
C2	0.030 (1)	0.037 (1)	0.020 (1)	−0.0064 (9)	0.007 (1)	−0.003 (1)
C3	0.042 (1)	0.036 (1)	0.025 (1)	−0.004 (1)	0.006 (1)	0.010 (1)
C4	0.034 (1)	0.034 (1)	0.022 (1)	0.003 (1)	−0.005 (1)	0.007 (1)
C5	0.029 (1)	0.028 (1)	0.018 (1)	0.0031 (8)	0.0002 (9)	−0.0018 (9)
C6	0.040 (1)	0.047 (2)	0.018 (1)	0.009 (1)	−0.002 (1)	0.006 (1)
C7	0.031 (1)	0.046 (1)	0.026 (1)	0.007 (1)	0.005 (1)	−0.006 (1)
C8	0.041 (1)	0.031 (1)	0.034 (1)	−0.005 (1)	−0.003 (1)	−0.012 (1)
C9	0.030 (1)	0.0248 (10)	0.041 (2)	0.0024 (9)	0.005 (1)	0.000 (1)
B	0.025 (1)	0.028 (1)	0.041 (2)	−0.0067 (9)	0.005 (1)	−0.005 (2)

Geometric parameters (Å, º)

P—C1	1.843 (4)	C2—C3	1.518 (5)
P—C4	1.829 (4)	C3—C4	1.539 (5)
P—C5	1.851 (4)	C5—C6	1.523 (5)
P—B	1.926 (4)	C5—C7	1.538 (5)
C1—C2	1.536 (5)	C5—C8	1.539 (5)
C1—C9	1.523 (4)
C1—P—C4	95.7 (2)	C1—C2—C3	107.6 (3)
C1—P—C5	107.8 (2)	C2—C3—C4	107.4 (3)
C1—P—B	116.2 (2)	P—C4—C3	105.7 (2)
C4—P—C5	109.8 (2)	P—C5—C6	107.7 (2)
C4—P—B	112.0 (2)	P—C5—C7	108.2 (2)
C5—P—B	113.9 (2)	P—C5—C8	111.9 (3)
P—C1—C2	103.5 (2)	C6—C5—C7	110.3 (3)
P—C1—C9	114.4 (2)	C6—C5—C8	109.8 (3)
C2—C1—C9	114.1 (3)	C7—C5—C8	108.9 (3)
P—C1—C2—C3	40.3 (3)	C3—C4—P—C5	103.4 (3)
P—C4—C3—C2	32.5 (3)	C3—C4—P—B	−129.0 (3)
C1—P—C4—C3	−7.8 (3)	C4—P—C1—C9	−143.1 (3)
C1—P—C5—C6	−60.4 (3)	C4—P—C5—C6	−163.4 (3)
C1—P—C5—C7	−179.6 (2)	C4—P—C5—C7	77.3 (3)
C1—P—C5—C8	60.4 (3)	C4—P—C5—C8	−42.7 (3)
C1—C2—C3—C4	−48.5 (4)	C5—P—C1—C9	104.1 (3)
C2—C1—P—C4	−18.2 (2)	C6—C5—P—B	70.1 (3)
C2—C1—P—C5	−131.1 (2)	C7—C5—P—B	−49.2 (3)
C2—C1—P—B	99.8 (3)	C8—C5—P—B	−169.2 (2)
C3—C2—C1—C9	165.3 (3)	C9—C1—P—B	−25.1 (4)

(III)

Crystal data

C16H38B2P2	Dx = 1.017 Mg m^−3
Mr = 314.04	Cu Kα radiation, λ = 1.5418 Å
Monoclinic, C2/c	Cell parameters from 20 reflections
a = 10.346 (1) Å	θ = 22.1–24.7°
b = 9.796 (2) Å	µ = 1.82 mm^−1
c = 20.597 (1) Å	T = 296 K
β = 100.805 (8)°	Prismatic, colorless
V = 2050.5 (4) Å^3	0.48 × 0.30 × 0.20 mm
Z = 4

Data collection

Rigaku AFC5S diffractometer	Rint = 0.022
ω–2θ scans	θmax = 67.6°
Absorption correction: ψ scan (North et al., 1968)	h = 0→12
Tmin = 0.517, Tmax = 0.695	k = 0→11
1945 measured reflections	l = −24→24
1839 independent reflections	3 standard reflections every 150 reflections
1376 reflections with F^2 > 2.0σ(F^2)	intensity decay: 0.8%

Refinement

Refinement on F	w = 1/[σ^2(Fo) + 0.00022|Fo|^2]
R[F^2 > 2σ(F^2)] = 0.048	(Δ/σ)max = 0.0.1
wR(F^2) = 0.058	Δρmax = 0.23 e Å^−3
S = 1.79	Δρmin = −0.18 e Å^−3
1423 reflections	Extinction correction: Zachariasen (1967) type 2 Gaussian isotropic
92 parameters	Extinction coefficient: 0.086 (5)
H-atom parameters not refined

Special details

Refinement. Refinement using reflections with F² > 1.0 σ(F²). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
P	0.66094 (7)	0.29673 (8)	0.59162 (4)	0.0462 (2)
C1	0.6933 (2)	0.2183 (3)	0.5141 (1)	0.0389 (7)
C2	0.5587 (3)	0.2298 (3)	0.4673 (1)	0.0485 (8)
C3	0.4512 (3)	0.1997 (3)	0.5066 (2)	0.0568 (9)
C4	0.4812 (3)	0.2888 (3)	0.5677 (2)	0.0592 (9)
C5	0.7094 (3)	0.1790 (4)	0.6625 (1)	0.0608 (10)
C6	0.6601 (5)	0.2441 (6)	0.7210 (2)	0.120 (2)
C7	0.8565 (4)	0.1658 (5)	0.6803 (2)	0.098 (1)
C8	0.6471 (4)	0.0393 (4)	0.6490 (2)	0.104 (2)
B	0.7180 (4)	0.4822 (4)	0.6071 (2)	0.072 (1)
H1	0.6828	0.5212	0.6426	0.0872*
H2	0.8134	0.4854	0.6198	0.0872*
H3	0.6932	0.5363	0.5688	0.0872*
H4	0.7184	0.1114	0.5239	0.0564*
H5	0.5532	0.1667	0.4315	0.0592*
H6	0.5469	0.3200	0.4495	0.0592*
H7	0.4534	0.1048	0.5184	0.0680*
H8	0.3667	0.2199	0.4811	0.0680*
H9	0.4456	0.3778	0.5587	0.0721*
H10	0.4442	0.2499	0.6029	0.0721*
H11	0.5539	0.0448	0.6364	0.1239*
H12	0.6791	−0.0043	0.6119	0.1239*
H13	0.6691	−0.0203	0.6858	0.1239*
H14	0.5648	0.2570	0.7100	0.1503*
H15	0.6971	0.3342	0.7303	0.1503*
H16	0.6792	0.1910	0.7595	0.1503*
H17	0.8969	0.2515	0.6891	0.1203*
H18	0.8892	0.1236	0.6442	0.1203*
H19	0.8803	0.1079	0.7181	0.1203*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0395 (4)	0.0523 (4)	0.0485 (4)	−0.0033 (4)	0.0127 (3)	−0.0061 (4)
C1	0.033 (1)	0.039 (1)	0.045 (1)	−0.001 (1)	0.008 (1)	−0.002 (1)
C2	0.036 (1)	0.057 (2)	0.052 (2)	−0.004 (1)	0.007 (1)	−0.007 (1)
C3	0.032 (1)	0.068 (2)	0.070 (2)	−0.003 (1)	0.010 (1)	−0.004 (2)
C4	0.038 (1)	0.075 (2)	0.068 (2)	0.005 (2)	0.020 (1)	−0.003 (2)
C5	0.055 (2)	0.081 (2)	0.046 (2)	−0.009 (2)	0.007 (1)	0.007 (2)
C6	0.137 (4)	0.173 (5)	0.059 (2)	0.004 (4)	0.043 (3)	0.008 (3)
C7	0.063 (2)	0.152 (4)	0.072 (2)	−0.008 (2)	−0.006 (2)	0.045 (3)
C8	0.110 (3)	0.094 (3)	0.094 (3)	−0.032 (3)	−0.016 (3)	0.042 (3)
B	0.072 (3)	0.055 (2)	0.094 (3)	−0.006 (2)	0.027 (2)	−0.022 (2)

Geometric parameters (Å, º)

P—C1	1.859 (3)	C2—C3	1.522 (4)
P—C4	1.834 (3)	C3—C4	1.516 (4)
P—C5	1.854 (3)	C5—C6	1.534 (5)
P—B	1.919 (4)	C5—C7	1.503 (5)
C1—C1^i	1.534 (4)	C5—C8	1.515 (5)
C1—C2	1.542 (4)
C1—P—C4	95.1 (1)	C1—C2—C3	108.6 (2)
C1—P—C5	110.7 (1)	C2—C3—C4	105.9 (2)
C1—P—B	115.8 (2)	P—C4—C3	106.7 (2)
C4—P—C5	107.2 (1)	P—C5—C6	106.2 (3)
C4—P—B	110.5 (2)	P—C5—C7	111.0 (2)
C5—P—B	115.4 (2)	P—C5—C8	112.0 (2)
P—C1—C1^i	115.5 (2)	C6—C5—C7	108.3 (3)
P—C1—C2	102.7 (2)	C6—C5—C8	109.1 (3)
C1—C1^i—C2	113.6 (3)	C7—C5—C8	110.1 (3)
P—C1—C1^i—P^i	180.0	C2—C1—P—C4	15.6 (2)
P—C1—C1^i—C2^i	61.7 (3)	C2—C1—P—C5	126.2 (2)
P—C1—C2—C3	−39.4 (3)	C2—C1—P—B	−100.0 (2)
P—C4—C3—C2	−35.6 (3)	C2—C1—C1^i—C2^i	180.0
C1—P—C4—C3	11.3 (2)	C3—C4—P—C5	−102.2 (2)
C1—P—C5—C6	−171.8 (3)	C3—C4—P—B	131.3 (2)
C1—P—C5—C7	70.7 (3)	C4—P—C5—C6	−69.3 (3)
C1—P—C5—C8	−52.8 (3)	C4—P—C5—C7	173.2 (3)
C1—C1^i—P^i—C4^i	−139.8 (3)	C4—P—C5—C8	49.7 (3)
C1—C1^i—P^i—C5^i	109.7 (3)	C6—C5—P—B	54.2 (3)
C1—C1^i—P^i—B^i	−24.1 (3)	C7—C5—P—B	−63.3 (3)
C1—C1^i—C2^i—C3^i	164.9 (3)	C8—C5—P—B	173.2 (3)
C1—C2—C3—C4	50.1 (3)

Symmetry code: (i) −x+3/2, −y+1/2, −z+1.